Methods for making wet gels and dried gels therefrom

ABSTRACT

Methods for making wet gels and dried gels therefrom are provided. The method for making a wet gel can include combining a hydroxybenzene compound, an aldehyde compound, and an additive to produce a reaction mixture. The additive can include a carboxylic acid, an anhydride, a homopolymer, a copolymer, or any mixture thereof. At least the hydroxybenzene compound and the aldehyde compound can be reacted to produce a wet gel. The reaction mixture can include about 10 wt % to about 65 wt % of the hydroxybenzene compound, about 5 wt % to about 25 wt % of the aldehyde compound, up to about 85 wt % of the carboxylic acid, up to about 40 wt % of the anhydride, up to about 40 wt % of the homopolymer, and up to about 40 wt % of the copolymer, where weight percent values are based on the combined weight of the hydroxybenzene compound, the aldehyde compound, and the additive.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Provisional Patent ApplicationSer. No. 61/880,199, filed on Sep. 20, 2013, which is incorporated byreference herein.

BACKGROUND

Field

Embodiments described generally relate to methods for making wet gelsand dried gels therefrom. More particularly, such embodiments relate tomethods for making wet gels that can be processed into dried gels andcarbon products.

Description of the Related Art

Carbon-containing wet gels and dried gels provided therefrom, such ascarbon aerogels, xerogels, and cryogels, have been used in a variety ofproducts to improve properties including, but not limited to, thermalinsulation value, electrical conductivity, and energy storage. Methodsfor synthesizing wet gels and converting the wet gels into aerogels,cryogels, and xerogels are known in the art, and depending on theparticular drying method the end product is typically referred to as anaerogel, a cryogel, or a xerogel. One particular composition caninclude, for example, resorcinol and formaldehyde (a “monomer component”or “sol,” which is a solution or a colloidal dispersion of particles ina liquid) for producing precursor solutions that can be furtherprocessed into a large monolithic polymer gel or “sol-gel.”

For many applications, aerogels (which are dried gels) having pores withdiameters between about 2 nm and 50 nm (mesoporous) or larger, are thepreferred end product. The monolithic polymer gels, however, aredifficult and expensive to convert into an aerogel. For example,supercritical drying, the drying process typically used to makeaerogels, requires specialized equipment and is time consuming andexpensive.

There is a need, therefore, for improved methods for making wet gelsthat can be processed to produce dried gels and carbon products.

SUMMARY

Methods for making wet gels and dried gels and carbon products therefromare provided. In at least one specific embodiment, a method for making awet gel, can include combining a hydroxybenzene compound, an aldehydecompound, and an additive to produce a reaction mixture. The additivecan include a carboxylic acid, an anhydride, a homopolymer, a copolymer,or any mixture thereof. The method can also include reacting at leastthe hydroxybenzene compound and the aldehyde compound to produce a wetgel. The reaction mixture can include about 10 wt % to about 65 wt % ofthe hydroxybenzene compound, about 5 wt % to about 25 wt % of thealdehyde compound, up to about 85 wt % of the carboxylic acid, up toabout 40 wt % of the anhydride, up to about 40 wt % of the homopolymer,and up to about 40 wt % of the copolymer. The reaction mixture caninclude about 10 wt % to about 90 wt % of the additive, where all weightpercent values are based on the combined weight of the hydroxybenzenecompound, the aldehyde compound, and the additive.

In at least one specific embodiment, a method for making a dried gel caninclude combining a solvent, a hydroxybenzene compound, an aldehydecompound, and an additive to produce a reaction mixture. The additivecan include a carboxylic acid, an anhydride, a homopolymer, a copolymer,or any mixture thereof. At least the hydroxybenzene compound and thealdehyde compound can be reacted to produce a wet gel. The method canalso include drying the wet gel to produce a dried gel. A pressureexerted on the wet gel during drying can be maintained below a criticalpressure of the solvent. The dried gel can have an average pore size ofabout 10 nm to about 150 nm, a specific surface area of about 5 m²/g toabout 1,500 m²/g, a pore volume of about 0.2 cm³/g to about 2.5 cm³/g,or any combination thereof.

In at least one other specific embodiment, the method for making a driedgel, can include determining one or more desired properties of a driedgel. The one or more desired properties can include an average pore sizeof about 10 nm to about 150 nm, a specific surface area of about 5 m²/gto about 1,500 m²/g, a pore volume of about 0.2 cm³/g to about 2.5cm³/g, or any combination thereof. The method can also include combininga solvent, a hydroxybenzene compound, an aldehyde compound, and anadditive to produce a reaction mixture. The additive can include acarboxylic acid, an anhydride, a homopolymer, a copolymer, or anymixture thereof. At least the hydroxybenzene compound and the aldehydecompound can be reacted to produce a wet gel. The method can alsoinclude drying the wet gel to produce a dried gel. A pressure exerted onthe wet gel during drying can be maintained below a critical pressure ofthe solvent. At least one of the amount of the hydroxybenzene compound,the amount of the aldehyde compound, and the amount of the additive canbe controlled to produce the dried gel having the one or more desiredproperties.

DETAILED DESCRIPTION

A wet gel can be formed by reacting or polymerizing a reactant orreaction mixture that can include, but is not limited to, at least onehydroxybenzene compound, at least one aldehyde compound, and at leastone additive. The additive can include, but is not limited to, at leastone carboxylic acid, at least one anhydride, at least one homopolymer,at least one copolymer, or any mixture thereof. The wet gel can also beformed by reacting or polymerizing a reaction mixture that can include,but is not limited to, a prepolymer and the additive. The prepolymer canbe formed by reacting the at least one hydroxybenzene compound and theat least one aldehyde compound. The prepolymer can further polymerize inthe presence of the additive such that the additive does not reactand/or does react to form part of the polymer forming the wet gel. Assuch, the polymer can be free from the at least one additive. Saidanother way, the polymer can be composed of only the reaction productbetween the at least one hydroxybenzene compound and the at least onealdehyde compound. The reaction mixture can also include, but is notlimited to, the hydroxybenzene compound, the aldehyde compound, theprepolymer, and the additive.

As used herein, the term “wet gel” refers to a wet (aqueous ornon-aqueous based) network of polymer chains that have one or more poresor voids therein and a liquid at least partially occupying or fillingthe one or more pores or voids. If the liquid that at least partiallyoccupies or fills the voids is water, the polymer particles can bereferred to as a “hydrogel.” As used herein, the term prepolymer refersto the reaction product formed by reacting at least the hydroxybenzenecompound and the aldehyde compound with one another so long as theresulting product remains in liquid form at room temperature (e.g.,about 25° C.).

The reaction mixture can also include, but is not limited to, at leastone solvent and/or at least one catalyst. Any one or more of thecomponents of the reaction mixture can be reactive or non-reactive. Forexample, the hydroxybenzene compound and the aldehyde compound can reactwith one another to form a polymer. In another example, the solvent canbe non-reactive with any of the other components of the reactionmixture.

The wet gel, such as polymer particles in gel form or a monolithicpolymer structure in gel form, can be produced by polymerizing thereaction mixture in a solution, dispersion, suspension, and/or emulsionprocess. The reaction or polymerization of the reaction mixture canproceed via a sol gel-type process to produce the wet gel. The sol gelprocess is a process that can be used to produce wet gels in amonolithic form. The sol gel process is discussed and described in, forexample, U.S. Pat. Nos. 4,873,218; 4,997,804; 5,124,364; and 5,556,892.The reaction or polymerization of the reaction mixture can proceed viastep-growth polymerization, e.g., condensation polymerization, additionpolymerization, or a combination of step-growth and additionpolymerization. The reaction or polymerization of the reaction mixtureand/or the formation of the prepolymer can be carried out in one or moresolvents or liquid mediums.

As used herein, the term “solvent” refers to a substance that dissolvesor suspends the reactants and provides a medium in which a reaction mayoccur. Suitable solvents can include, but are not limited to, water, oneor more alcohols, one or more alkanes, one or more ketones, one or morearomatic hydrocarbons, or any mixture thereof. Illustrative alcohols caninclude, but are not limited to, methanol, ethanol, propanol, t-butanol,or any mixture thereof. Illustrative alkanes can include, but are notlimited to, hexane, heptane, octane, nonane, decane, and the like,isomers thereof, or any mixture thereof. Illustrative ketones caninclude, but are not limited to, acetone, benzophenone, acetophenone,2,2-dimethyl-1,3-cyclopentanedione, or any mixture thereof. Othersuitable solvents can include, but are not limited to, tetrahydrofuran,benzene, toluene, xylene, ethylbenzene, cumene, mesitylene, or anymixture thereof. The liquid that at least partially occupies or fillsthe pores or voids of the wet gel can be or include the solvent. Theliquid that at least partially occupies or fills the pores or voids ofthe wet gel can also include one or more of the reactants in thereaction mixture (the hydroxybenzene compound, the aldehyde compound,and the additive, e.g., the carboxylic acid, the anhydride, thehomopolymer, the copolymer, and/or the catalyst). In at least oneembodiment, the intentional addition of a solvent can be avoided.Additionally, if the solvent is not added to the reaction mixture, ifthe hydroxybenzene compound and the aldehyde compound react with oneanother via a condensation reaction, the water generated from thecondensation reaction can become or serve as a solvent or liquid thatcan at least partially occupy or fill the pores or voids of the wet gel.

The reaction or polymerization of the reaction mixture can proceed via asuspension or dispersion polymerization process to produce the wet gel.As used herein, the terms “suspension process,” “suspensionpolymerization process,” “dispersion process,” and “dispersionpolymerization process” are used interchangeably and refer to aheterogeneous reaction process that uses mechanical agitation to mix thereaction mixture in the solvent or “continuous phase” fluid such as ahydrocarbon and/or water, where the reaction mixture phase and thesolvent or continuous phase fluid are not miscible. The reaction mixturecan be suspended or dispersed in the solvent or continuous phase asdroplets, where the reactants (at least the hydroxybenzene compound andthe aldehyde compound) can undergo reaction to form particles of polymerand/or curing to form cured particles of polymer. As used herein, theterm “curing” refers to the toughening or hardening of polymers via anincreased degree of cross-linking of polymer chains. Cross-linkingrefers to the structural and/or morphological change that occurs in thepre-polymer and/or polymer, such as by covalent chemical reaction, ionicinteraction or clustering, phase transformation or inversion, and/orhydrogen bonding.

The reaction or polymerization of the reaction mixture can proceed viaan emulsion polymerization process to produce the wet gel. As usedherein, the terms “emulsion process” and “emulsion polymerizationprocess” refer to both “normal” emulsions and “inverse” emulsions.Emulsions differ from suspensions in one or more aspects. One differenceis that an emulsion will usually include the use of a surfactant thatcreates or forms the emulsions (very small size droplets). When thecarrier or continuous phase fluid is a hydrophilic fluid, such as water,and the reaction mixture phase is a hydrophobic compound(s), normalemulsions, such as oil-in-water, form, where droplets of monomers areemulsified with the aid of a surfactant in the carrier or continuousphase fluid. Monomers react in these small size droplets. These dropletsare typically small in size as the particles are stopped fromcoagulating with each other because each particle is surrounded by thesurfactant and the charge on the surfactant electrostatically repelsother particles. Whereas suspension polymerization usually creates muchlarger particles than those made with emulsion polymerization. When thecarrier or continuous phase fluid is a hydrophobic fluid such as oil andthe reaction mixture phase is hydrophilic compounds, inverse-emulsions,such as water-in-oil, form.

Illustrative suspension and emulsion polymerization processes suitablefor preparing the wet gel can include those discussed and described inU.S. Patent Application Publication Nos.: 2013/0211005 and 2014/0148560and U.S. Provisional Patent Application Ser. No. 61/731,113, filed onNov. 29, 2012.

In one or more embodiments, the preparation of the wet gel particles canbe controlled such that two or more populations of particle sizedistributions can be produced. For example, introduction of an aqueousphase to an organic phase can be staged. As such, the final wet gelparticle distribution can include one or two or more nodes, where theratio between the highest and lowest node can be about 1,000 or lower,about 500 or lower, about 200 or lower, about 100 or lower, about 50 orlower, about 25 or lower, about 10 or lower, 5 or lower, or about 2 orlower. For example, the ratio between the highest node and the lowestnode can be about 0.1, about 0.5, about 1, about 2, about 3, about 5,about 7, or about 10 to about 30, about 60, about 90, about 125, about150, about 250, about 400, about 600, about 700, about 800, about 900,or about 950.

The hydroxybenzene compound and the aldehyde compound can bepre-polymerized at a temperature from a low of about 20° C., about 25°C., about 30° C., about 35° C., or about 40° C. to a high of about 50°C., about 55° C., about 60° C., about 65° C., about 70° C., about 75°C., about 80° C., about 85° C., about 90° C., about 95° C., about 100°C., 150° C., about 200° C., about 250° C., or about 300° C. In one ormore embodiments, the hydroxybenzene compound and the aldehyde compoundcan be pre-polymerized under pressure and the temperature during theprepolymerization can be up to the boiling point of the reactionmixture. For example, the hydroxybenzene compound and the aldehydecompound can be pre-polymerized at a temperature of about 30° C. toabout 95° C., about 60° C. to about 90° C., about 75° C. to about 95°C., or about 50° C. to about 90° C. In another example, thehydroxybenzene compound and the aldehyde compound can be pre-polymerizedat a temperature of about 40° C., about 50° C., about 60° C., about 70°C., about 75° C., about 80° C., about 85° C., about 90° C., or about 95°C. The prepolymer can be mixed, blended, stirred, or otherwise combinedwith at least one of and the additive, with or without the solventand/or catalyst.

If the prepolymer is formed by reacting the hydroxybenzene compound withthe aldehyde compound, the extent or amount the compounds react to formthe prepolymer can be based on one or more properties. Illustrativeproperties of the reaction product or prepolymer that can be used tomonitor the extent of reaction can include, but are not limited to,viscosity, water concentration, refractive index, the unreacted or freeconcentration of the aldehyde compound, molecular weight, or anycombination thereof.

If the prepolymer is formed, the hydroxybenzene compound and thealdehyde compound can be reacted with one another until the prepolymerhas a viscosity from a low of about 0.5 cP, about 1 cP, about 2 cP,about 10 cP, or about 50 cP to a high of about 100 cP, about 500 cP,about 1,000 cP, about 2,500 cP, about 5,000 cP, or about 10,000 cP at atemperature of 25° C. For example, the hydroxybenzene and aldehyde canbe reacted with one another until the prepolymer has a viscosity ofabout 1 cP to about 800 cP, about 5 cP to about 500 cP, about 75 cP toabout 400 cP, about 125 cP to about 1,100 cP, or about 150 cP to about300 cP at a temperature of 25° C. The viscosity of the reaction mixtureor prepolymer or other liquids can be determined using a BrookfieldViscometer at a temperature of 25° C. For example, the BrookfieldViscometer can be equipped with a small sample adapter such a 10 mLadapter and the appropriate spindle to maximize torque such as a spindleno. 31.

If the prepolymer is formed, the hydroxybenzene compound and thealdehyde compound can be reacted with one another until the prepolymerhas a water concentration from a low of about 0.5 wt %, about 1 wt %,about 2 wt %, or about 3 wt % to a high of about 50 wt %, about 60 wt %,about 70 wt %, or about 80 wt %, based on the weight of the prepolymer,any unreacted hydroxybenzene compound, any unreacted aldehyde compound,and water. For example, the prepolymer can be produced by reactingphenol and formaldehyde, and the formaldehyde combined with the phenolcan be a 50 wt % aqueous solution. As such, the water concentration canbe based on water produced or generated during formation of theprepolymer and/or water added to the mixture of phenol and formaldehyde,water present with the hydroxybenzene compound, and/or water presentwith the aldehyde compound. The hydroxybenzene compound and the aldehydecompound can be reacted with one another to produce the prepolymer withthe reaction reduced or stopped and/or the carboxylic acid, theanhydride, the homopolymer, and/or the copolymer added thereto when theprepolymer has a water concentration from about 5 wt % to about 50 wt %,about 1 wt % to about 25 wt %, about 10 wt % to about 40 wt %, about 12wt % to about 20 wt %, or about 15 wt % to about 35 wt %, based on theweight of the prepolymer, any unreacted hydroxybenzene compound, anyunreacted aldehyde compound, and water.

If the prepolymer is formed, the hydroxybenzene compound and thealdehyde compound can be reacted to an endpoint based on the refractiveindex of the liquid prepolymer. For example, the prepolymer can bepolymerized until the prepolymer has a refractive index from a low ofabout 1.1000, about 1.2000, about 1.3000, or about 1.3200 to a high ofabout 1.4500, about 1.4800, about 1.5000, about 1.5500, about 1.6000,about 1.6500, about 1.7000, about 1.7500, or about 1.8000. In anotherexample, the polymerization of the monomer mixture to produce theprepolymer can be carried out to a refractive index of about 1.3500 toabout 1.4500, about 1.3800 to about 1.4400, about 1.3900 to about1.4350, about 1.3900 to about 1.4500, about 1.1000 to about 1.7000,about 1.3000 to about 1.6000, about 1.4200 to about 1.5500, about 1.4800to about 1.6400, or about 1.3700 to about 1.4300.

If the prepolymer is formed, the hydroxybenzene compound and thealdehyde compound can be reacted with one another to an endpoint basedon the unreacted or free concentration of the aldehyde compound. Forexample, the prepolymer can be polymerized until the reaction mixturehas no free aldehyde compound remaining or an unreacted or freeconcentration of the aldehyde compound from a low of about 0.5 wt %,about 1 wt %, about 3 wt %, or about 5 wt % to a high of about 10 wt %,about 15 wt %, about 20 wt %, or about 25 wt %. In another example, theprepolymer can be polymerized until the reaction mixture has anunreacted or free concentration of the aldehyde compound of about 2 wt %to about 17 wt %, about 1 wt % to about 5 wt %, about 4 wt % to about 12wt %, or about 6 wt % to about 18 wt %.

If the prepolymer is formed, the hydroxybenzene compound and thealdehyde compound can be reacted with one another to an endpoint basedon the molecular weight of the prepolymer. For example, the prepolymercan be polymerized until the prepolymer has a weight average molecularweight from a low of about 100, about 300, about 500, or about 800 to ahigh of about 1,000, about 5,000, about 10,000, or about 20,000. Inanother example, the prepolymer can be polymerized until the prepolymerhas a weight average molecular weight of about 200 to about 1,200, about400 to about 900, about 600 to about 2,500, about 1,000 to about 6,000,about 3,000 to about 12,000, or about 7,000 to about 16,000.

In one or more embodiments, the reaction mixture can be agitated. Forexample, the reaction mixture can be agitated to improve and/or maintaina homogeneous or substantially homogenous distribution of the reactantsin the solvent or a homogeneous or substantially homogenous distributionof the solvent in the reaction mixture. In one or more embodiments, thereaction mixture is not agitated. The components of the reaction mixturecan be combined within one or more mixers. The mixer can be or includeany device, system, or combination of device(s) and/or system(s) capableof batch, intermittent, and/or continuous mixing, blending, contacting,or the otherwise combining of two or more components. Illustrativemixers can include, but are not limited to, mechanical mixer agitation,ejectors, static mixers, mechanical/power mixers, shear mixers, sonicmixers, vibration mixing, movement of the mixer itself, or anycombination thereof. The mixer can include one or more heating jackets,heating coils, internal heating elements, cooling jackets, coolingcoils, internal cooling elements, or the like, to regulate thetemperature therein. The mixer can be an open vessel or a closed vessel.The components of the reaction mixture can be combined within the mixerunder a vacuum, at atmospheric pressure, or at pressures greater thanatmospheric pressure.

Depending, at least in part, on the temperature at which reactionbetween the components of the reaction mixture is carried out; thereactants can react and/or cure in a time ranging from about 30 secondsto several days. For example, the reaction mixture can be reacted and/orcured in a time ranging from a low of about 1 minute, about 2 minutes,about 3 minutes, about 4 minutes, about 5 minutes, about 10 minutes,about 15 minutes, or about 20 minutes to a high of about 40 minutes,about 1 hour, about 1.5 hours, about 2 hours, about 3 hours, about 4hours, about 5 hours, about 10 hours, about 15 hours, about 20 hours,about 1 day, about 2 days, about 3 days, about 4 days, about 5 days,about 6 days, or more to produce the wet gel. The reaction mixture canbe reacted and/or cured at a temperature from a low of about 25° C.,about 35° C., about 45° C., about 55° C., or about 65° C. to a high ofabout 85° C., about 100° C., about 125° C., about 150° C., about 175°C., about 200° C., about 225° C., about 250° C., about 275° C., or about300° C. The pressure of the reaction mixture during reaction can be froma vacuum to greater than atmospheric pressure. For example, the pressureof the reaction mixture during reaction can be from a low of about 50kPa, about 75 kPa, about 100 kPa, or atmospheric pressure to a high ofabout 200 kPa, about 500 kPa, about 5,000 kPa, about 10,000 kPa, orabout 50,000 kPa.

The reaction between at least the hydroxybenzene compound and thealdehyde compound and/or the prepolymer in the presence of the additivecan be carried out in one continuous reaction step or two or morereaction steps. One example of a multi-step reaction process can includeheating the reactants to a first temperature for a first period of timein the reaction vessel to produce a first or intermediate product. Theintermediate product can then be heated or cooled to a secondtemperature for a second period of time to produce the wet gel product.The second temperature can be greater than the first temperature or lessthan the first temperature. The second period of time can be greaterthan the first period of time or less than the first period of time.Another example of a multi-step reaction process can include heating thereactants to a first temperature for a first period of time in thereaction vessel to produce a first or intermediate product. Theintermediate product can be heated to a second temperature for a secondperiod of time to produce a second intermediate product. The secondintermediate product can then be heated to a third temperature for athird period of time to produce the wet gel. The third temperature canbe greater than the second temperature or less than the secondtemperature. The third temperature can be greater than the firsttemperature or less than the first temperature. If the reaction mixtureis heated within a sealed reaction vessel during the production of thewet gel, the pressure within the—reaction vessel may increase duringheating of the reaction mixture. The wet gel can be made in a reactionvessel that remains open (not sealed), closed (sealed), or the reactionvessel can be open for some of the time and closed for some of the time.The pressure of the reaction mixture, the first intermediate product,and/or the second intermediate product can be anywhere from less thanatmospheric pressure to greater than atmospheric pressure.

In at least one specific example, the hydroxybenzene compound and thealdehyde compound and/or the prepolymer formed therefrom and theadditive can be combined in the reaction vessel to form a reactionmixture and the reaction mixture can be heated to a first temperaturefor a first period of time to produce a first intermediate product. Theone or more catalyst and/or solvents can also be added to the reactionvessel and be present in the reaction mixture. The first temperature canbe from a low of about 25° C., about 30° C., about 35° C., about 40° C.,about 45° C., about 50° C., or about 60° C. to a high of about 80° C.,about 90° C., about 95° C., about 100° C. or more. The first period oftime can be from a low of about 30 minutes, about 1 hour, about 1.5hours, about 2 hours, or about 3 hours to a high of about 6 hours, about12 hours, about 18 hours, about 1 day, about 2 days, about 3 days, ormore than about 3 days. The first intermediate product can then heatedto a second temperature for a second period of time to produce a secondintermediate product. The second temperature can be from a low of about25° C., about 30° C., about 35° C., about 40° C., about 45° C., about50° C., or about 60° C. to a high of about 80° C., about 90° C., about95° C., about 100° C. or more. The second period of time can be from alow of about 30 minutes, about 1 hour, about 1.5 hours, about 2 hours,or about 3 hours to a high of about 6 hours, about 12 hours, about 18hours, about 1 day, about 2 days, about 3 days, or more than 3 days. Thesecond intermediate product can be heated to a third temperature for athird period of time to produce the wet gel. The third temperature canbe from a low of about 25° C., about 30° C., about 35° C., about 40° C.,about 45° C., about 50° C., or about 60° C. to a high of about 80° C.,about 90° C., about 95° C., about 100° C. or more. The third period oftime can be from a low of about 30 minutes, about 1 hour, about 1.5hours, about 2 hours, or about 3 hours to a high of about 6 hours, about12 hours, about 18 hours, about 1 day, about 2 days, or about 3 days.

If the solvent is present in the reaction mixture, the temperature ofthe reaction mixture, the first intermediate product, the secondintermediate product, and/or any other intermediate products formedbefore arriving at the wet gel product can be maintained at atemperature below the boiling point of the solvent. If the solvent ispresent in the reaction mixture, the temperature of the reactionmixture, the first intermediate product, the second intermediateproduct, and/or any other intermediate products formed before arrivingat the wet gel product can be increased above the boiling point of thesolvent during heating of any one or more of the reaction mixture, thefirst intermediate product, the second intermediate product, and/or anyother intermediate products.

The reaction between the components of the reaction mixture, e.g., atleast the hydroxybenzene compound and the aldehyde compound, can becarried out under a wide range of pH values. For example, the reactionbetween the components of the reaction mixture can be carried out at apH of a low of about 1, about 2, or about 3 to a high of about 7, about8, about 9, about 10, about 11, or about 12. In one or more embodiments,the reaction can be carried out under acidic conditions. For example,the pH of the reaction mixture can be less than 7, less than 6.5, lessthan 6, less than 5.5, less than 5, less than 4.5, or less than 4. Inanother example, the pH of the reaction mixture can range from about 1to about 6.5, about 1.5 to about 5.5, about 2 to about 5, about 1.5 toabout 4.5, about 1 to about 4, about 2 to about 4, about 1 to about 3.5,or about 2 to about 4.5.

The molar ratio of the hydroxybenzene compound to the aldehyde compoundcan be from a low of about 0.1:1, about 0.3:1, about 0.5:1, about 0.7:1,or about 1:1 to a high of about 1.5:1, about 1.7:1, or about 2:1. Forexample, the molar ratio of the one or more hydroxybenzene compound tothe aldehyde compounds can be from about 0.1:1 to about 1.8:1, about0.2:1 to about 1.4:1, about 0.8:1 to about 1.3:1, about 0.2:1 to about0.9:1, about 0.3:1 to about 0.8:1, about 0.4:1 to about 0.8:1, about0.4:1 to about 0.7:1, or about 0.4:1 to about 0.6:1. In at least oneexample, the molar ratio of the hydroxybenzene compound to the aldehydecompound can be about 0.4:1, about 0.5:1, about 0.6:1, about 0.7:1,about 0.8:1, about 0.9:1, about 1:1, about 1.1:1, about 1.2:1, about1.3:1, about 1.4:1, or about 1.5:1.

If the catalyst is present, the molar ratio of the hydroxybenzenecompound to the catalyst can be from a low of about 2:1, about 3:1,about 4:1, about 5:1, about 6:1, or about 7:1 to a high of about 50:1,about 100:1, about 200:1, about 500:1, or about 1,000:1. For example,the molar ratio of the hydroxybenzene compound to catalyst can be fromabout 2:1 to about 1,000:1, about 3:1 to about 800:1, a about 4:1 toabout 700:1, about 5:1 to about 300:1, about 2:1 to about 50:1, about1:1 to about 20:1, about 10:1 to about 30:1, about 20:1 to about 40:1,or about 30:1 to about 50:1. In another example, the molar ratio of thehydroxybenzene compound can be at least 2:1, at least 3:1, at least 4:1,at least 5:1, at least 10:1, at least 15:1, at least 25:1, at least40:1, at least 55:1, at least 60:1, at least 65:1, at least 70:1, or atleast 75:1 and less than 1,000:1, less than 500:1, less than 200:1, orless than 100:1.

The reaction mixture can include from a low of about 5 wt %, about 10 wt%, about 15 wt %, about 20 wt %, about 25 wt %, or about 30 wt % to ahigh of about 45 wt %, about 50 wt %, about 55 wt %, about 60 wt %,about 65 wt %, or about 70 wt % of the hydroxybenzene compound, based onthe combined weight of the hydroxybenzene compound, the aldehydecompound, and the additive. For example, the reaction mixture caninclude about 10 wt % to about 50 wt %, about 15 wt % to about 45 wt %,about 17 wt % to about 40 wt %, or about 20 wt % to about 35 wt % of thehydroxybenzene compound, based on the combined weight of thehydroxybenzene compound, the aldehyde compound, and the additive. Inanother example, the reaction mixture can include at least 12 wt %, atleast 15 wt %, at least 17 wt %, or at least 20 wt % to about 35 wt %,about 40 wt %, about 45 wt %, or about 50 wt % of the hydroxybenzenecompound, based on the combined weight of the hydroxybenzene compound,the aldehyde compound, and the additive.

The reaction mixture can include from a low of about 3 wt %, about 5 wt%, about 7 wt %, about 9 wt %, or about 10 wt % to a high of about 11 wt%, about 12 wt %, about 14 wt %, about 16 wt %, about 18 wt %, about 20wt %, about 22 wt %, about 25 wt %, or about 30 wt % of the aldehydecompound, based on the combined weight of the hydroxybenzene compound,the aldehyde compound, and the additive. For example, the reactionmixture can include about 6 wt % to about 22 wt %, about 7 wt % to about18 wt %, about 8 wt % to about 17 wt %, or about 9 wt % to about 16 wt %of the aldehyde compound, based on the combined weight of thehydroxybenzene compound, the aldehyde compound, and the additive. Inanother example, the reaction mixture can include at least 5 wt %, atleast 6 wt %, at least 7 wt %, or at least 8 wt % to about 14 wt %,about 16 wt %, about 18 wt %, or about 20 wt % of the aldehyde compound,based on the combined weight of the hydroxybenzene compound, thealdehyde compound, and the additive.

The reaction mixture can include from low of about 0.1 wt %, about 1 wt%, about 3 wt %, about 5 wt %, about 7 wt %, about 10 wt %, about 12 wt%, or about 15 wt % to a high of about 40 wt %, about 50 wt %, about 60wt %, about 70 wt %, about 80 wt %, or about 85 wt % of the carboxylicacid, based on the combined weight of the hydroxybenzene compound, thealdehyde compound, and the additive. For example, the reaction mixturean include about 10 wt % to about 75 wt %, about 20 wt % to about 45 wt%, about 35 wt % to about 65 wt %, about 50 wt % to about 70 wt %, about25 wt % to about 35 wt %, about 30 wt % to about 45 wt %, or about 55 wt% to about 65 wt % of the carboxylic acid, based on the combined weightof the hydroxybenzene compound, the aldehyde compound, and the additive.In another example, the reaction mixture can include at least 20 wt %,at least 25 wt %, at least 30 wt %, or at least 35 wt % to about 60 wt%, about 65 wt %, about 70 wt %, or about 75 wt % of the carboxylicacid, based on the combined weight of the hydroxybenzene compound, thealdehyde compound, and the additive.

The reaction mixture can include from a low of about 0.1 wt %, about 1wt %, about 3 wt %, about 5 wt %, about 7 wt %, about 10 wt %, about 12wt %, or about 15 wt % to a high of about 20 wt %, about 25 wt %, about30 wt %, about 35 wt %, or about 40 wt % of the anhydride, based on thecombined weight of the hydroxybenzene compound, the aldehyde compound,and the additive. For example, reaction mixture can include about 0.5 wt% to about 6 wt %, about 1 wt % to about 5 wt %, about 1.5 wt % to about3 wt %, about 5 wt % to about 15 wt %, about 10 wt % to about 25 wt %,about 20 wt % to about 40 wt %, about 10 wt % to about 35 wt %, or about1 wt % to about 8 wt % of the anhydride, based on the combined weight ofthe hydroxybenzene compound, the aldehyde compound, and the additive. Inanother example, the reaction mixture can include at least 0.5 wt %, atleast 1 wt %, at least 1.5 wt %, or at least 2 wt % to about 5 wt %,about 10 wt %, about 20 wt %, or about 30 wt % of the anhydride, basedon the combined weight of the hydroxybenzene compound, the aldehydecompound, and the additive.

The reaction mixture can include from a low of about 0.1 wt %, about 1wt %, about 3 wt %, about 5 wt %, about 7 wt %, about 10 wt %, about 12wt %, or about 15 wt % to a high of about 20 wt %, about 25 wt %, about30 wt %, about 35 wt %, or about 40 wt % of the homopolymer, based onthe combined weight of the hydroxybenzene compound, the aldehydecompound, and the additive. For example, the reaction mixture caninclude about 0.5 wt % to about 6 wt %, about 1 wt % to about 5 wt %,about 1.5 wt % to about 3 wt %, about 5 wt % to about 15 wt %, about 10wt % to about 25 wt %, about 20 wt % to about 40 wt %, about 10 wt % toabout 35 wt %, or about 1 wt % to about 8 wt % of the homopolymer, basedon the combined weight of the hydroxybenzene compound, the aldehydecompound, and the additive. In another example, the reaction mixture caninclude at least 0.5 wt %, at least 1 wt %, at least 1.5 wt %, or atleast 2 wt % to about 5 wt %, about 10 wt %, about 20 wt %, or about 30wt % of the homopolymer, based on the combined weight of thehydroxybenzene compound, the aldehyde compound, and the additive.

The reaction mixture can include from a low of about 0.1 wt %, about 1wt %, about 3 wt %, about 5 wt %, about 7 wt %, about 10 wt %, about 12wt %, or about 15 wt % to a high of about 20 wt %, about 25 wt %, about30 wt %, about 35 wt %, or about 40 wt % of the copolymer, based on thecombined weight of the hydroxybenzene compound, the aldehyde compound,and the additive. For example, the reaction mixture can include about0.5 wt % to about 6 wt %, about 1 wt % to about 5 wt %, about 1.5 wt %to about 3 wt %, about 5 wt % to about 15 wt %, about 10 wt % to about25 wt %, about 20 wt % to about 40 wt %, about 10 wt % to about 35 wt %,or about 1 wt % to about 8 wt % of the copolymer, based on the combinedweight of the hydroxybenzene compound, the aldehyde compound, and theadditive. In another example, the reaction mixture can include at least0.5 wt %, at least 1 wt %, at least 1.5 wt %, or at least 2 wt % toabout 5 wt %, about 10 wt %, about 20 wt %, or about 30 wt % of thecopolymer, based on the combined weight of the hydroxybenzene compound,the aldehyde compound, and the additive.

The reaction mixture can include from a low of about 1 wt %, about 3 wt%, about 5 wt %, about 8 wt %, about 10 wt %, about 15 wt %, about 20 wt%, about 30 wt %, or about 35 wt % to a high of about 50 wt %, about 60wt %, about 70 wt %, about 80 wt %, or about 90 wt % of the additive,based on the combined weight of the hydroxybenzene compound, thealdehyde compound, and the additive. Said another way, the total amountof the additive (the combined amount(s) of carboxylic acid, anhydride,homopolymer, and copolymer) can be from a low of about 1 wt %, about 3wt %, about 5 wt %, about 8 wt %, about 10 wt %, about 15 wt %, about 20wt %, about 30 wt %, or about 35 wt % to a high of about 50 wt %, about60 wt %, about 70 wt %, about 80 wt %, or about 90 wt % of the additive,based on the combined weight of the hydroxybenzene compound, thealdehyde compound, and the additive(s). For example, the reactionmixture can include about 50 wt % to about 80 wt %, about 60 wt % toabout 75 wt %, about 2 wt % to about 30 wt %, about 15 wt % to about 50wt %, about 20 wt % to about 45 wt %, about 35 wt % to about 65 wt %,about 55 wt % to about 75 wt %, about 70 wt % to about 85 wt %, or about30 wt % to about 45 wt % of the additive, based on the combined weightof the hydroxybenzene compound, the aldehyde compound, and the additive.In another example, the reaction mixture can include at least 10 wt %,at least 15 wt %, at least 20 wt %, at least 25 wt %, at least 30 wt %,at least 35 wt %, at least 40 wt %, at least 45 wt %, at least 50 wt %,at least 55 wt %, or at least 60 wt % to about 65 wt %, about 70 wt %,about 75 wt %, about 80 wt %, or about 90 wt % of the additive, based onthe combined weight of the hydroxybenzene compound, the aldehydecompound, and the additive.

In one or more embodiments, the reaction mixture can include theadditive in an amount from a low of about 10 wt %, about 15 wt %, about20 wt %, about 25 wt %, about 30 wt %, about 35 wt %, about 40 wt %,about 45 wt %, about 50 wt %, about 55 wt %, or about 60 wt % to a highof about 65 wt %, about 70 wt %, about 75 wt %, about 80 wt %, or about90 wt %, where the reaction mixture includes up to about 65 wt %, up toabout 70 wt %, up to about 75 wt %, or up to about 85 wt % of thecarboxylic acid, up to about 25 wt %, up to about 30 wt %, up to about35 wt %, or up to about 40 wt % of the anhydride, up to about 25 wt %,up to about 30 wt %, up to about 35 wt %, or up to about 40 wt % of thehomopolymer, and up to about 25 wt %, up to about 30 wt %, up to about35 wt %, or up to about 40 wt % of the copolymer, where all weightpercent values are based on the combined weight of the hydroxybenzenecompound, the aldehyde compound, and the additive. For example, thereaction mixture can include up to about 85 wt % of the carboxylic acid,up to about 40 wt % of the anhydride, up to about 40 wt % of thehomopolymer, and up to about 40 wt % of the copolymer, where thereaction mixture includes about 10 wt % to about 90 wt % of theadditive, where all weight percent values are based on the combinedweight of the hydroxybenzene compound, the aldehyde compound, and theadditive. In another example, the reaction mixture can include theadditive in an amount of about 10 wt %, about 15 wt %, about 20 wt %,about 25 wt %, about 30 wt %, about 35 wt %, about 40 wt %, about 45 wt%, about 50 wt %, about 55 wt %, or about 60 wt % to about 65 wt %,about 70 wt %, about 75 wt %, about 80 wt %, or about 90 wt %; thecarboxylic acid in an amount of 85 wt % or less, 75 wt % or less, 70 wt% or less, or 60 wt % or less; the anhydride in an amount of 40 wt % orless, 35 wt % or less, 30 wt % or less, or 25 wt % or less; thehomopolymer in an amount of 40 wt % or less, 35 wt % or less, 30 wt % orless, or 25 wt % or less; and the copolymer in an amount of 40 wt % orless, 35 wt % or less, 30 wt % or less, or 25 wt % or less, where allweight percent values are based on the combined weight of thehydroxybenzene compound, the aldehyde compound, and the additive.

The reaction mixture can include from a low of about 1 wt %, about 5 wt%, about 10 wt %, about 15 wt %, about 20 wt %, about 25 wt %, about 30wt %, about 35 wt %, about 40 wt %, or about 45 wt % to a high of about60 wt %, about 65 wt %, about 70 wt %, about 75 wt %, about 80 wt %,about 85 wt %, about 90 wt %, or about 95 wt % of the solvent, based onthe combined weight of the hydroxybenzene compound, the aldehydecompound, the solvent, the catalyst, and the additive. For example, thereaction mixture can include about 1 wt % to about 95 wt %, about 5 wt %to about 90 wt %, about 10 wt % to about 85 wt %, or about 15 wt % toabout 75 wt % of the solvent, based on the combined weight of thehydroxybenzene compound, the aldehyde compound, the solvent, thecatalyst, and the additive. In another example, the reaction mixture caninclude at least 1 wt %, at least 5 wt %, at least 10 wt %, at least 15wt %, or at least 20 wt % to about 60 wt %, about 65 wt %, about 70 wt%, about 75 wt %, about 80 wt %, about 85 wt %, about 90 wt %, or about95 wt % of the solvent, based on the combined weight of thehydroxybenzene compound, the aldehyde compound, the solvent, thecatalyst, and the additive. In still another example, the reactionmixture can include from a low of about 1 wt %, about 5 wt %, about 10wt %, about 15 wt %, about 20 wt %, about 25 wt %, about 30 wt %, about35 wt %, about 40 wt %, or about 45 wt % to a high of about 60 wt %,about 65 wt %, about 70 wt %, about 75 wt %, about 80 wt %, about 85 wt%, about 90 wt %, or about 95 wt % of the solvent, based on the combinedweight of the hydroxybenzene compound, the aldehyde compound, theadditive, and the solvent.

The hydroxybenzene compound can be or include substituted phenoliccompounds, unsubstituted phenolic compounds, or any combination ormixture of substituted and/or unsubstituted phenolic compounds. Forexample, the hydroxybenzene compound can be or include, but is notlimited to, phenol, resorcinol (1,3-dihydroxybenzene), or a combinationor mixture thereof. In another example, the hydroxybenzene compound canalso be or include any compound or combination of compounds, from whichresorcinol or any resorcinol derivative can be derived. In anotherexample, the hydroxybenzene compound can be a monohydroxybenzene, adihydroxybenzene, a trihydroxybenzene, any other polyhydroxybenzene, orany combination or mixture thereof. In another example, thehydroxybenzene compound can be phenol.

In one or more embodiments, the hydroxybenzene compound can berepresented by Formula I:

where each R₁ can independently be selected from hydrogen, a hydroxy, aC1-C5 alkyl, or OR′, where R′ can be a C1-C5 alkyl or a C1-C5 aryl.Other suitable hydroxybenzene compounds can be represented by FormulaII:

where each R₃ can independently be selected from hydrogen; a hydroxy; ahalide such as fluoride, chloride, bromide, or iodide; a nitro; a benzo;a carboxy; an acyl such as formyl, an alkyl-carbonyl such as acetyl, andan arylcarbonyl such as benzoyl; alkyl such as methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and the like; analkenyl such as unsubstituted or substituted vinyl and allyl;unsubstituted or substituted methacrylate, unsubstituted or substitutedacrylate; silyl ether; siloxanyl; aryl such as phenyl and naphthyl;aralkyl such as benzyl; or alkyaryl such as alkylphenols, and where atleast two R₃ can be hydrogen.

Other suitable hydroxybenzene compounds can include, but are not limitedto, alkyl-substituted phenols such as the cresols and xylenols;cycloalkyl-substituted phenols such as cyclohexyl phenol;alkenyl-substituted phenols; aryl-substituted phenols such as p-phenylphenol; alkoxy-substituted phenols such as 3,5-dimethyoxyphenol; aryloxyphenols such as p-phenoxy phenol; and halogen-substituted phenols suchas p-chlorophenol. Dihydric phenols such as catechol, resorcinol,hydroquinone, bisphenol A and bisphenol F also can also be used. Inparticular, the hydroxybenzene compound can be phenol; resorcinol;catechol; hydroquinone; alkyl-substituted phenols such as the cresolsand xylenols; cycloalkyl-substituted phenols such as cyclohexyl phenol;alkenyl-substituted phenols; aryl-substituted phenols such as p-phenylphenol; alkoxy-substituted phenols such as 3,5-dimethyoxyphenol; aryloxyphenols such as p-phenoxy phenol; halogen-substituted phenols such asp-chlorophenol; bisphenol A; and bisphenol F; or any combination ormixture thereof. Still other suitable hydroxybenzene compounds can be orinclude pyrogallol; 5-methylresorcinol; 5-ethylresorcinol;5-propylresorcinol; 4-methylresorcinol; 4-ethylresorcinol;4-propylresorcinol; resorcinol monobenzoate; resorcinol monosinate;resorcinol diphenyl ether; resorcinol monomethyl ether; resorcinolmonoacetate; resorcinol dimethyl ether; phloroglucinol;benzoylresorcinol; resorcinol rosinate; alkyl substituted resorcinol;aralkyl substituted resorcinol such as 2-methylresorcinol;phloroglucinol; 1,2,4-benzenetriol; 3,5-dihydroxybenzaldehyde;2,4-dihydroxybenzaldehyde; 4-ethylresorcinol; 2,5-dimethylresorcinol;5-methylbenzene-1,2,3-triol, 3,5-dihydroxybenzyl alcohol;2,4,6-trihydroxytoluene; 4-chlororesorcinol;2′,6′-dihydroxyacetophenone; 2′,4′-dihydroxyacetophenone;3′,5′-dihydroxyacetophenone; 2,4,5-trihydroxybenzaldehyde;2,3,4-trihydroxybenzaldehyde; 2,4,6-trihydroxybenzaldehyde;3,5-dihydroxybenzoic acid; 2,4-dihydroxybenzoic acid;2,6-dihydroxybenzoic acid; 1,3-dihydroxynaphthalene;2′,4′-dihydroxypropiophenone; 2′,4′-dihydroxy-6′-methylacetophenone;1-(2,6-dihydroxy-3-methylphenyl)ethanone; 3-methyl3,5-dihydroxybenzoate; methyl 2,4-dihydroxybenzoate; gallacetophenone;2,4-dihydroxy-3-methylbenzoic acid; 2,6-dihydroxy-4-methylbenzoic acid;methyl 2,6-dihydroxybenzoate; 2-methyl-4-nitroresorcinol;2,4,5-trihydroxybenzoic acid; 3,4,5-trihydroxybenzoic acid;2,3,4-trihydroxybenzoic acid; 2,4,6-trihydroxybenzoic acid;2-nitrophloroglucinol; or any combination or mixture thereof. Anothersuitable hydroxybenzene compound can be or include phloroglucinol.

In one or more embodiments, the hydroxybenzene compound can also be orinclude one or more tannins. As used herein, the term “tannin” refers toboth hydrolyzable tannins and condensed tannins. As such, thehydroxybenzene compound can be or include hydrolyzable tannins,condensed tannins, or a combination of hydrolyzable tannins andcondensed tannins. Illustrative genera of shrubs and/or trees from whichsuitable tannins can be derived can include, but are not limited to,Acacia, Castanea, Vachellia, Senegalia, Terminalia, Phyllanthus,Caesalpinia, Quercus, Schinopsis, Tsuga, Rhus, Juglans, Carya, andPinus, or any combination or mixture thereof. In another example, generafrom which suitable tannins can be derived can include, but are notlimited to, Schinopsis, Acacia, or a combination or mixture thereof. Inanother example, genera from which suitable tannins can be derived caninclude, but are not limited to, Pinus, Carya, or a combination ormixture thereof.

Hydrolyzable tannins are mixtures of simple phenols such as pyrogalloland ellagic acid and of esters of a sugar such as glucose, with gallicand digallic acids. Illustrative hydrolyzable tannins can include, butare not limited to, extracts recovered from Castanea sativa (e.g.,chestnut), Terminalia and Phyllanthus (e.g., myrabalans tree species),Caesalpinia coriaria (e.g., divi-divi), Caesalpinia spinosa, (e.g.,tara), algarobilla, valonea, and Quercus (e.g., oak). Condensed tanninsare polymers formed by the condensation of flavans. Condensed tanninscan be linear or branched molecules. Illustrative condensed tannins caninclude, but are not limited to Acacia mearnsii (e.g., wattle or mimosabark extract), Schinopsis (e.g., quebracho wood extract), Tsuga (e.g.,hemlock bark extract), Rhus (e.g., sumach extract), Juglans (e.g.,walnut), Carya illinoinensis (e.g., pecan), and Pinus (e.g., Radiatapine, Maritime pine, or bark extract species).

The condensed tannins include about 70 wt % to about 80 wt % activephenolic ingredients (the “tannin fraction”) and the remainingingredients (the “non-tannin fraction”) can include, but are not limitedto, carbohydrates, hydrocolloid gums, and amino and/or imino acidfractions. The condensed tannins can be used as recovered or extractedfrom the organic matter and/or the condensed tannins can be purified,e.g., to about 95 wt % or more active phenolic ingredients. Hydrolyzabletannins and condensed tannins can be extracted from the startingmaterial, e.g., trees and/or shrubs, using well established processes. Amore detailed discussion of tannins is discussed and described in theHandbook of Adhesive Technology, Second Edition, CRC Press, 2003,chapter 27, “Natural Phenolic Adhesives I: Tannin,” and in Monomers,Polymers and Composites from Renewable Resources, Elsevier, 2008,chapter 8, “Tannins: Major Sources, Properties and Applications.”

The condensed tannins can be classified or grouped into one of two maincategories, namely, those containing a resorcinol unit and thosecontaining a phloroglucinol unit. Illustrative tannins that include theresorcinol unit include, but are not limited to, black wattle tanninsand quebracho tannins. Illustrative tannins that include thephloroglucinol unit include, but are not limited to, pecan tannins andpine tannins.

Suitable aldehyde compounds can be represented by Formula III:

where R₄ can be a hydrogen, an alkyl, an alkenyl, or an alkynyl. Thealkyl, alkenyl, or alkynyl can include 1 carbon atom to about 8 carbonatoms. In another example, suitable aldehyde compounds can also includethe so-called masked aldehydes or aldehyde equivalents, such as acetalsor hemiacetals. Illustrative aldehyde compounds can include, but are notlimited to, formaldehyde, paraformaldehyde, acetaldehyde,propionaldehyde, butyraldehyde, furfuraldehyde, benzaldehyde, or anycombination or mixture thereof. One or more other aldehydes, such asglyoxal can be used in place of or in combination with formaldehydeand/or other aldehydes. In at least one example, the aldehyde compoundcan include formaldehyde, UFC, or a combination or mixture thereof.

The aldehyde compounds can be used as in solid, liquid, and/or gasstates. Considering formaldehyde in particular, the formaldehyde can beor include paraformaldehyde (solid, polymerized formaldehyde), formalinsolutions (aqueous solutions of formaldehyde, sometimes with methanol,in about 37 wt %, about 44 wt %, or about 50 wt % formaldehydeconcentrations), Urea-Formaldehyde Concentrate (“UFC”), and/orformaldehyde gas in lieu of or in addition to other forms offormaldehyde can also be used. In another example, the aldehyde can beor include a pre-reacted urea-formaldehyde mixture having a urea toformaldehyde weight ratio of about 1:2 to about 1:3.

The aldehyde compound can also be or include, but is not limited to, oneor more multifunctional aldehyde compounds. As used herein, the terms“multifunctional aldehyde compound” and “multifunctional aldehyde” areused interchangeably and refer to compounds having at least twofunctional groups, with at least one of the functional groups being analdehyde group. For example, the multifunctional aldehyde can includetwo or more aldehyde functional groups. In another example, themultifunctional aldehyde can include at least one aldehyde functionalgroup and at least one functional group other than an aldehydefunctional group. As used herein, the term “functional group” refers toreactive groups in the multifunctional aldehyde compound and caninclude, but is not limited to, aldehyde groups, carboxylic acid groups,ester groups, amide groups, imine groups, epoxide groups, aziridinegroups, azetidinium groups, and hydroxyl groups.

The multifunctional aldehyde compound can include two or more carbonatoms and can include two or more aldehyde functional groups. Forexample, the multifunctional aldehyde compound can include two, three,four, five, six, or more carbon atoms and have two or more aldehydefunctional groups. The multifunctional aldehyde compound can include twoor more carbon atoms and have at least one aldehyde functional group andat least one functional group other than an aldehyde group such as acarboxylic acid group, an ester group, an amide group, an imine groups,an epoxide group, an aziridine group, an azetidinium group, and/or ahydroxyl group. For example, the multifunctional aldehyde compound caninclude two, three, four, five, six, or more carbon atoms and have atleast one aldehyde functional group and at least one functional groupother than an aldehyde group such as a carboxylic acid group, an estergroup, an amide group, an imine group, an epoxide group, an aziridinegroup, an azetidinium group, and/or a hydroxyl group. It should be notedthat a multi-functional aldehyde compound having an aldehyde group and acarboxylic acid group could be considered as the aldehyde compound orthe carboxylic acid compound, but such a multi-functional aldehydecompound is not intended to satisfy both simultaneously. Said anotherway, the hydroxybenzene compound, the aldehyde compound, and thecarboxylic acid, the anhydride, the homopolymer, and/or the copolymerrefer to different compounds with respect to one another.

Suitable bifunctional or difunctional aldehydes that include three (3)or more carbon atoms and have two aldehyde functional groups (—CHO) canbe represented by Formula IV:

where R₅ can be an alkenylene, an alkenylene, an alkynyl, acycloalkenylene, a cycloalkenylene, a cycloalkynyl, or an arylene,having 1 carbon atom to about 12 carbon atoms. Illustrativemulti-functional aldehydes can include, but are not limited to,malonaldehyde, succinaldehyde, glutaraldehyde, 2-hydroxyglutaraldehyde,β-methylglutaraldehyde, adipaldehyde, pimelaldehyde, suberaldehyde,malealdehyde, fumaraldehyde, sebacaldehyde, phthalaldehyde,isophthalaldehyde, terephthalaldehyde, ring-substituted aromaticaldehydes, or any combination or mixture thereof. A suitablebifunctional or difunctional aldehyde that includes two carbon atoms andhas two aldehyde functional groups is glyoxal.

Illustrative multifunctional aldehyde compounds that include an aldehydegroup and a functional group other than an aldehyde group can include,but are not limited to, glyoxylic acid, glyoxylic acid esters, glyoxylicacid amides, 5-(hydroxymethyl)furfural, or any combination or mixturethereof. The aldehyde group in the multifunctional aldehyde compound canexist in other forms, e.g., as a hydrate. As such, any form orderivative of a particular multifunctional aldehyde compound can be usedto prepare the wet gels discussed and described herein. The aldehydecompound can include any combination of two or more aldehyde compoundscombined with one another and/or added independent of one another to thereaction mixture.

The carboxylic acid can include, but is not limited to, monocarboxylicacids, dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids,pentacarboxylic acids, carboxylic acids having more than five carboxylgroups, polymeric polycarboxylic acids, and any combination or mixturethereof. The monocarboxylic acid can be represented by Formula V:

where R₆ can be an alkyl, alkenyl, or alkynyl carbon chain having 1carbon atom to about 50 carbon atoms. Illustrative monocarboxylic acidscan include, but are not limited to, methanoic acid or formic acid,ethanoic acid or acetic acid, propanoic acid, butanoic acid, petanoicacid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid,decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid,tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, hexadecanoicacid, heptadecanoic acid, octadecanoic acid, icosanoic acid, acrylicacid, or any combination or mixture thereof.

The dicarboxylic acid can be represented by Formula VI:

where R₇ can be an alkylene, alkenylene, or alkynyl carbon chain having1 carbon atom to about 50 carbon atoms.

The tricarboxylic acid can be represented by Formula VIIR₈(COOH)₃   (VII)

where R₈ can be an alkylene, alkenylene, or an alkynyl carbon chainhaving 1 carbon atom to about 50 carbon atoms.

The dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids,pentacarboxylic acids, and carboxylic acids having six or morecarboxylic acid groups can be referred to collectively as“polycarboxylic acids.” Suitable polycarboxylic acids can include, butare not limited to, unsaturated aliphatic dicarboxylic acids, saturatedaliphatic dicarboxylic acids, aromatic dicarboxylic acids, unsaturatedcyclic dicarboxylic acids, saturated cyclic dicarboxylic acids,hydroxy-substituted derivatives thereof, and the like. Other suitablepolycarboxylic acids can include unsaturated aliphatic tricarboxylicacids, saturated aliphatic tricarboxylic acids such as citric acid,aromatic tricarboxylic acids, unsaturated cyclic tricarboxylic acids,saturated cyclic tricarboxylic acids, hydroxy-substituted derivativesthereof, and the like. It is appreciated that any such polycarboxylicacids can be optionally substituted, such as with hydroxy, halo, alkyl,alkoxy, and the like.

Illustrative polycarboxylic acids can include, but are not limited to,citric acid, ethanedioic acid, propanedioic acid, butanedioic acid,petanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid,nonanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioicacid, or any combination or mixture thereof. Other illustrativedicarboxylic acids can include, but are not limited to, (Z)-butenedioicacid or maleic acid, (E)-butenedioic acid or fumaric acid,pent-2-enedioic acid or glutaconic acid, dodec-2-enedioic acid ortraumatic acid, (2E,4E)-hexa-2,4-dienedioic acid or muconic acid, citricacid, isocitric acid, aconitic acid, adipic acid, azelaic acid, butanetetracarboxylic acid dihydride, butane tricarboxylic acid, chlorendicacid, citraconic acid, dicyclopentadiene-maleic acid adducts,diethylenetriamine pentaacetic acid, adducts of dipentene and maleicacid, ethylenediamine tetraacetic acid (EDTA), fully maleated rosin,maleated tall-oil fatty acids, fumaric acid, glutaric acid, isophthalicacid, itaconic acid, maleated rosin oxidized with potassium peroxide toalcohol then carboxylic acid, maleic acid, malic acid, mesaconic acid,biphenol A or bisphenol F reacted via the KOLBE-Schmidt reaction withcarbon dioxide to introduce 3-4 carboxyl groups, oxalic acid, phthalicacid, sebacic acid, succinic acid, tartaric acid, terephthalic acid,tetrabromophthalic acid, tetrachlorophthalic acid, tetrahydrophthalicacid, trimellitic acid, trimesic acid, or any combination or mixturethereof.

Suitable polymeric polycarboxylic acids can include organic polymers oroligomers containing more than one pendant carboxyl group. The polymericpolycarboxylic acid can be a homopolymer or copolymer prepared fromunsaturated carboxylic acids that can include, but are not limited to,acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleicacid, cinnamic acid, 2-methylmaleic acid, itaconic acid,2-methylitaconic acid, α,β-methyleneglutaric acid, and the like. Thepolymeric polycarboxylic acid can also be prepared from unsaturatedanhydrides. Unsaturated anhydrides can include, but are not limited to,maleic anhydride, itaconic anhydride, acrylic anhydride, methacrylicanhydride, and the like, as well as mixtures thereof.

Polymeric polycarboxylic acids can include polyacrylic acid,polymethacrylic acid, polymaleic acid, and the like. Examples ofcommercially available polyacrylic acids include AQUASET® 529 (Rohm &Haas, Philadelphia, Pa., USA), Criterion 2000 (Kemira, Helsinki,Finland, Europe), NF1 (H. B. Fuller, St. Paul, Minn., USA), and SOKALAN®(BASF, Ludwigshafen, Germany, Europe). With respect to SOKALAN®, this isbelieved to be a water-soluble polyacrylic copolymer of acrylic acid andmaleic acid, having a molecular weight of approximately 4,000. AQUASET®529 is understood to be a composition containing polyacrylic acidcross-linked with glycerol, also containing sodium hypophosphite as acatalyst. Criterion 2000 is thought to be an acidic solution of apartial salt of polyacrylic acid, having a molecular weight ofapproximately 2,000. NF1 is believed to be a copolymer containingcarboxylic acid functionality and hydroxy functionality, as well asunits with neither functionality; NF1 is also thought to contain chaintransfer agents, such as sodium hypophosphite or organophosphatecatalysts.

The anhydride can be represented by Formula VII:

where each R₉ and R₁₀ can independently be an alkyl, alkenyl, or alkynylcarbon chain, having 1 carbon atom to about 50 carbon atoms. In one ormore embodiments, R₉ and R₁₀ can be bonded together to form a cyclicstructure. Illustrative anhydrides can include, but are not limited to,maleic anhydride, phthalic anhydride, acetic anhydride, succinicanhydride, styrene maleic anhydride, naphthalic anhydride,1,2,4-benzenetricarboxylic anhydride, or any combination or mixturethereof.

In addition to the carboxylic acid homopolymers, other suitablehomopolymers can include, but are not limited to, polyethylene,polypropylene, polystyrene, polyvinylchloride, or any combination ormixture thereof.

In addition to the carboxylic acid copolymers, other suitable copolymerscan include, but are not limited to, alternating copolymers, periodiccopolymers, statistical copolymers, terpolymers, block copolymers,linear copolymers, branched copolymers, or any combination or mixturethereof. The alternating copolymer can be represented by the formula:˜ABABABABABABABAB˜. Illustrative alternating copolymers can include, butare not limited to, poly[styrene-alt-(maleic anhydride)], poly[(ethyleneglycol)-alt-(terephthalic acid; isophthalic acid)], or a mixturethereof. The periodic copolymer can be represented by the formula:˜A-B-A-B-B-A-A-A-A-B-B-B-B˜. Illustrative periodic copolymers caninclude, but are not limited to, poly(1,3,6-trioxacyclooctane)poly(oxymethyleneoxyethyleneoxyethylene). The statistical copolymer canbe represented by the formula: ˜ABBAAABAABBBABAABA˜. Illustrativestatistical copolymers can include, but are not limited to,poly(styrene-stat-acrylonitrile-stat-butadiene), poly[(6-aminohexanoicacid)-stat-(7-aminoheptanoic acid)], poly[(4-hydroxybenzoicacid)-co-hydroquinone-co-(terephthalic acid)], poly[styrene-co-(methylmethacrylate)], or any combination or mixture thereof. Illustrativeterpolymers can include, but are not limited to,acrylonitrile-butadiene-styrene terpolymer, or any combination ormixture thereof. The block copolymer can be represented by the formula:˜AAAAA-BBBBBBB˜AAAAAAA˜BBB˜. Illustrative block copolymers can include,but are not limited to,polystyrene-block-polybutadiene-block-polystyrene, poly(ethyleneglycol)-poly(propylene glycol)-poly(ethylene glycol) block polymer,poly[poly(methyl methacrylate)-block-polystyrene-block-poly(methylacrylate)], or any combination or mixture thereof. Illustrative linearcopolymers can include, but are not limited to, a copolymer of ethyleneand one or more C₃ to C₂₀ alpha olefin comonomers copolymers, or anycombination or mixture thereof. Illustrative branched copolymers caninclude, but are not limited to, branched methacrylate copolymers.

In one or more embodiments, the reaction mixture can further include oneor more polyols. Suitable polyols can be represented by the followingFormula IX:R₁₁(OH)_(n)   (IX)

where R₁₁ can be a substituted or unsubstituted alkylene, a substitutedor unsubstituted alkenylene, a substituted or unsubstituted alkynylene,a substituted or unsubstituted cycloalkylene, a substituted orunsubstituted cycloalkenylene, a substituted or unsubstitutedcycloalkynylene, a substituted or unsubstituted heterocycloalkylene, asubstituted or unsubstituted heterocycloalkenylene, a substituted orunsubstituted heterocycloalkynylene, a substituted or unsubstitutedarylene, or a substituted or unsubstituted heteroarylene; and n is aninteger not less than 2. For example, n can be any integer from 2 to 10,2 to 50, or 2 to 100.

Illustrative polyols can include, but are not limited to,1,4-cyclohexanediol catechol, cyanuric acid, diethanolamine, pryogallol,butanediol, 1, 6-hexane diol, 1, 2, 6 hexanetriol, 1,3 butanediol,1,4-cyclohexane dimethanol, 2,2, 4 trimethylpentanediol, alkoxylatedbisphenol A, bis[N, N di beta-hydroxyethyl)] adipamid, bisphenol A,bisphenol A diglycidyl ether, bisphenol F diglycidyl ether,cyclohexanedimethanol, dibromoneopentyl glycol, polyglycerol, diethyleneglycol, dipropylene glycol, glycol ethers, ethoxylated DETA, ethyleneglycol, glycerine, neopentyl glycol, pentaerythritol, low molecularweight (e.g., a weight average molecular weight of about 750 or less)polyethylene glycol and/or polypropylene glycol, 1,3-propanediol,propylene glycol, polyethylene oxide (hydroxy terminated), sorbitol,tartaric acid, tetrabromoalkoxylate bisphenol A, tetrabromobisphenol A,tetrabromobisphenol diethoxy ether, triethanolamine, triethylene glycol,trimethylolethane, ethyle diethanolamine, methyl diethanolamine, one ormore carbohydrates, polyvinyl alcohols, hydroxyethylcellulose,resorcinol, pyrogallol, glycollated ureas, lignin, trimethylolpropane,tripropylene glycol, or any combination or mixture thereof. The one ormore carbohydrates can include one or more monosaccharides,disaccharides, oligosaccharides, polysaccharides, or any combination ormixture thereof.

One particular subclass of polyols can include carbohydrates. Suitablecarbohydrates can include monosaccharides, disaccharides,oligosaccharides, polysaccharides, or any combination or mixturethereof. The carbohydrate can include one or more aldose sugars. Themonosaccharide can be or include d-glucose (dextrose monohydrate),1-glucose, or a combination or mixture thereof. Other carbohydratealdose sugars can include, but are not limited to, glyceraldehyde,erythrose, threose, ribose, deoxyribose, arabinose, xylose, lyxose,allose, altrose, gulose, mannose, idose, galactose, talose, and anycombination or mixture thereof. The carbohydrate can also be or includeone or more reduced or modified starches such as dextrin, maltodextrin,and oxidized maltodextrins.

The reaction mixture can include from a low of about 0.1 wt %, about 1wt %, about 5 wt %, about 10 wt %, or about 15 wt % to a high of about25 wt %, about 30 wt %, about 35 wt %, about 40 wt %, or about 45 wt %of the polyol, based on the combined weight of the hydroxybenzenecompound, the aldehyde compound, the additive, and the polyol. Forexample, the reaction mixture can include about 0.5 wt % to about 15 wt%, about 5 wt % to about 20 wt %, about 10 wt % to about 30 wt %, about3 wt % to about 12 wt %, about 8 wt % to about 28 wt %, about 23 wt % toabout 35 wt %, about 4 wt % to about 12 wt %, or about 1 wt % to about20 wt % of the polyol, based on the combined weight of thehydroxybenzene compound, the aldehyde compound, the additive, and thepolyol. In another example, the reaction mixture can include at least0.1 wt %, at least 0.5 wt %, at least 1 wt %, at least 2 wt %, at least3 wt %, at least 4 wt %, at least 5 wt %, at least 7 wt %, or at least10 wt % to about 15 wt %, about 20 wt %, about 25 wt %, about 30 wt %,about 35 wt %, or about 40 wt % of the polyol, based on the combinedweight of the hydroxybenzene compound, the aldehyde compound, theadditive, and the polyol.

The solids content of the reaction mixture and/or the prepolymer canvary from a low of about 5%, about 10%, about 15%, about 20%, about 25%,about 35%, about 40%, or about 45% to a high of about 55%, about 60%,about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about95%, or about 99%. For example, the solids content of the reactionmixture and/or the prepolymer can be from about 35% to about 70%, about40% to about 60%, or about 45% to about 55%. In another example, thesolids content of the reaction mixture and/or the prepolymer can begreater than 20%, greater than 25%, greater than 30%, greater than 35%,greater than 40%, or great than 45%, great than 50%, great than 55%,great than 60%, great than 65%, great than 70%, great than 75%, greatthan 80%, great than 85%, or great than 90%. In another example, thesolids content of the reaction mixture and/or the prepolymer can be lessthan 90%, less than 85%, less than 80%, less than 75%, less than 70%,less than 65%, less than 60%, less than 55%, less than 50%, less than45%, less than 40%, less than 35%, less than 30%, less than 25%, lessthan 20%, or less than 15%.

The solids content of a composition, as understood by those skilled inthe art, can be measured by determining the weight loss upon heating asmall sample (e.g., about 1 gram to about 5 grams) of the composition,to a suitable temperature, e.g., 125° C., and a time sufficient toremove the liquid. By measuring the weight of the sample before andafter heating, the percent solids in the composition can be directlycalculated or otherwise estimated.

The catalyst can be combined with the reaction mixture to accelerate theformation of the prepolymer and/or the wet gel. The catalyst can be orinclude one or more acids, one or more bases, or any mixture thereof.Illustrative acid catalysts can include, but is not limited to,hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid,sulfonic acid (including but not limited to monosulfonic acid,disulfonic acid, trisulfonic acid, toluene sulfonic acid, and alkanesulfonic acid), gallic acid, oxalic acid, picric acid, or anycombination or mixture thereof. Other suitable acid catalyst can includeone or more of the carboxylic acids discussed and described above. Forexample, the acidic catalyst can be or include acetic acid, citric acid,or a mixture thereof. It should be noted that the catalyst, if present,may or may not react with one or more components of the reactionmixture.

Illustrative base catalysts can include, but are not limited to,hydroxides, carbonates, ammonia, amines, or any combination or mixturethereof. Illustrative hydroxides can include, but are not limited to,sodium hydroxide, potassium hydroxide, ammonium hydroxide (e.g., aqueousammonia), lithium hydroxide, cesium hydroxide, or any combination ormixture thereof. Illustrative carbonates can include, but are notlimited to, sodium carbonate, potassium carbonate, ammonium carbonate,or any combination or mixture thereof. Illustrative amines can include,but are not limited to, alkanolamines, polyamines, aromatic amines, andany combination or mixture thereof. Illustrative alkanolamines caninclude, but are not limited to, monoethanolamine (MEA), diethanolamine(DEA), triethanolamine (TEA), or any combination or mixture thereof.Illustrative alkanolamines can include, but are not limited to,diethanolamine, triethanolamine, 2-(2-aminoethoxyl)ethanol, aminoethylethanolamine, aminobutanol and other aminoalkanols. Illustrativearomatic amines can include, but are not limited to, benzyl amine,aniline, ortho-toluidine, meta-toluidine, para-toluidine, n-methylaniline, N—N′-dimethyl aniline, di phenyl amines and triphenyl amines,1-naphthylamine, 2-naphthylamine, 4-aminophenol, 3-aminophenol,2-aminophenol, or any combination or mixture thereof. Illustrativepolyamines can include, but are not limited to, diethylenetriamine(DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), orany combination or mixture thereof. Other polyamines can include, forexample, 1,3-propanediamine, 1,4-butanediamine, polyamidoamines,polyethylenimines, or any combination or mixture thereof.

Other suitable amines can include, but are not limited to, primaryamines (“NH₂R¹”), secondary amines (“NHR¹R²”), and tertiary amines(“NR¹R²R³”), where each R¹, R², and R³ can independently be selectedfrom alkyls, cycloalkyls, heterocycloalkyls, aryls, heteroaryls, andsubstituted aryls. The alkyl can include branched or unbranched alkylshaving 1 carbon atom to about 15 carbon atoms or 1 carbon atom to about8 carbon atoms. Illustrative alkyls can include, but are not limited to,methyl, ethyl, n-propyl, isopropyl, n-butyl, sec butyl, t-butyl,n-pentyl, n-hexyl, and ethylhexyl. The cycloalkyls can include 3 carbonatoms to about 7 carbon atoms. Illustrative cycloalkyls can include, butare not limited to, cyclopentyl, substituted cyclopentyl, cyclohexyl,and substituted cyclohexyl. The term “aryl” refers to an aromaticsubstituent containing a single aromatic ring or multiple aromatic ringsthat are fused together, linked covalently, or linked to a common groupsuch as a methylene or ethylene moiety. More specific aryl groups caninclude one aromatic ring or two or three fused or linked aromaticrings, e.g., phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, andthe like. In one or more embodiments, aryl substituents can have 1carbon atom to about 20 carbon atoms. The term “heteroatom-containing,”as in a “heteroatom-containing cycloalkyl group,” refers to a moleculeor molecular fragment in which one or more carbon atoms is replaced withan atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus,boron, or silicon. Similarly, the term “heteroaryl” refers to an arylsubstituent that is heteroatom-containing. The term “substituted,” as in“substituted aryls,” refers to a molecule or molecular fragment in whichat least one hydrogen atom bound to a carbon atom is replaced with oneor more substituents that are functional groups such as hydroxyl,alkoxy, alkylthio, phosphino, amino, halo, silyl, and the like.Illustrative primary amines can include, but are not limited to,methylamine and ethylamine. Illustrative secondary amines can include,but are not limited to, dimethylamine and diethylamine. Illustrativetertiary amines can include, but are not limited to, trimethylamine andtriethylamine Illustrative amides can include, but are not limited to,acetamide (ethanamide), dicyandiamide, and the like, or any combinationor mixture thereof.

In at least one example, the catalyst can be free or substantially freefrom any metal or metal ions. In other words, the catalyst can be anon-metal or non-metal ion containing catalyst. A catalyst that issubstantially free from any metal or metal ions can contain less than 1wt %, less than 0.5 wt %, less than 0.3 wt %, less than 0.2 wt %, lessthan 0.1 wt %, less than 0.7 wt %, less than 0.05 wt %, less than 0.3 wt%, less than 0.01 wt %, less than 0.007 wt %, less than 0.005 wt %, lessthan 0.003 wt %, less than 0.001 wt %, less than 0.0007 wt %, or lessthan 0.0005 wt %, based on the total weight of the catalyst.

The catalyst can be present in the reaction mixture in widely varyingamounts. For example, the reaction mixture can include from a low ofabout 0.01 wt %, about 0.05 wt %, about 0.1 wt %, about 0.5 wt %, about1 wt %, or about 1.5 wt % to a high of about 30 wt %, about 40 wt %,about 50 wt %, or about 60 wt % of the catalyst, based on the combinedweight of the hydroxybenzene compound, the aldehyde compound, thesolvent, the catalyst, and the additive. In another example, thereaction mixture can include from a low of about 0.01 wt %, about 0.02wt %, about 0.03 wt %, about 0.04 wt %, about 0.05 wt %, about 0.1 wt %,about 0.5 wt %, about 1 wt %, about 3 wt %, or about 5 wt % to a high ofabout 45 wt %, about 55 wt %, about 65 wt %, about 70 wt %, about 75 wt%, or about 80 wt % of the catalyst, based on the weight of thehydroxybenzene compound. In another example, the reaction mixture caninclude from a low of about 0.01 wt %, about 0.02 wt %, about 0.03 wt %,or about 0.04 wt % to a high of about 40 wt %, about 50 wt %, about 60wt %, about 70 wt %, or about 80 wt % of the catalyst, based on theweight of the aldehyde compound. In another example, the reactionmixture can include from a low of about 0.01 wt %, about 0.02 wt %,about 0.03 wt %, or about 0.04 wt % to a high of about 40 wt %, about 50wt %, about 60 wt %, or about 70 wt % of the catalyst, based on thecombined weight of the hydroxybenzene compound and the aldehydecompound.

If any one or more of the components discussed and described hereininclude two or more different compounds, those two or more differentcompounds can be present in any ratio with respect to one another. Forexample, if the hydroxybenzene includes a first hydroxybenzene compoundand a second hydroxybenzene compound, the hydroxybenzene compound canhave a concentration of the first hydroxybenzene compound ranging fromabout 0.1 wt % to about 99.9 wt % and conversely about 99.9 wt % toabout 0.1 wt % of the second hydroxybenzene compound, based on the totalweight of the first and second hydroxybenzene compounds. In anotherexample, the amount of the first hydroxybenzene compound can range froma low of about 5 wt %, about 10 wt %, about 15 wt %, about 20 wt %,about 25 wt % about 30 wt %, about 35 wt %, about 40 wt %, or about 45wt % to a high of about 60 wt %, about 65 wt %, about 70 wt %, about 75wt %, about 80 wt %, about 85 wt %, about 90 wt %, or about 95 wt %,based on the total weight of the first and second hydroxybenzenecompounds. When the aldehyde compound, carboxylic acid, anhydride,homopolymer, copolymer, catalyst, solvent, and/or any other componentincludes two or more different compounds, those two or more differentcompounds can be present in similar amounts as the first and secondhydroxybenzene compound.

If the wet gel is in the form of a monolithic structure, the monolithicstructure can have any desired shape. Typically the monolithic structurecan take the form or shape of the reaction vessel the wet gel isproduced or made in. For example, if the reaction vessel has an innercylindrical surface having a diameter of 25 cm, the monolithic wet gelmade in the reaction vessel can be in the form of a cylinder having adiameter of about 25 cm and a height corresponding to or dependent onthe amount of reactants added to the reaction vessel.

If the wet gel is in the form of a monolithic structure the monolithicstructure can be converted into particles. For example, the monolithicstructure can be ground, chopped, crushed, milled, or otherwise actedupon to provide a plurality of particulates or particles. Accordingly,the wet gel can be produced as a monolithic structure in the reactionvessel and dried as is or particulated prior to drying or the wet gelcan be directly produced as wet gel particles.

The wet gel particles can have an average cross-sectional length ofabout 0.1 μm, about 1 μm, about 100 μm, about 0.5 mm, about 1 mm, about1.5 mm, about 2 mm, about 2.5 mm, about 3 mm, about 3.5 mm, about 4 mm,about 4.5 mm, about 5 mm, about 5.5 mm, about 6 mm or more. For example,the wet gel particles can have an average cross-sectional length from alow of about 0.001 mm, about 0.01 mm, about 0.1 mm, about 0.5 mm, about1 mm, about 1.5 mm, about 2 mm, about 2.5 mm, about 3 mm, about 3.5 mm,or about 4 mm to a high of about 5 mm, about 7 mm, about 10 mm, about 12mm, about 15 mm, about 18 mm, about 20 mm, about 25 mm, about 30 mm ormore. In another example, the wet gel particles can have an averagecross-sectional length from a low of about 1 μm, about 10 μm, about 50μm, about 100 μm, about 200 μm, about 300 μm, about 500 μm, about 700μm, or about 1,000 μm to a high of about 1.1 mm, about 1.3 mm, about 1.5mm, about 2 mm, about 3 mm, about 4 mm, about 5 mm, about 7 mm, about 10mm, or more.

It has been surprisingly and unexpectedly discovered that reacting atleast the hydroxybenzene compound and the aldehyde compound with and/orin the presence of the carboxylic acid, the anhydride, the homopolymer,and/or the copolymer can produce a wet gel that can be converted to adried gel under a vacuum, at atmospheric pressure, or at a pressure thatis less than the supercritical pressure of any solvent present in thewet gel to produce a dried gel having one or more improved properties ascompared to a wet gel made in the absence of the carboxylic acid, theanhydride, the homopolymer, and/or the copolymer. The one or moreimproved properties can include, but are not limited to, an increasedpore volume, an increased pore size, an increased specific surface area,decreased density, or any combination or mixture thereof.

As used herein, the term “dried gel” refers to a network of polymerchains having one or more pores or voids therein and a gas occupying orfilling the one or more pores or voids. The gas can be or include, butis not limited to, oxygen, nitrogen, argon, helium, carbon monoxide,carbon dioxide, or any mixture thereof. In at least one specificexample, the gas occupying or filling the voids can be or include air.The dried gel can be or include a cured product. For example the driedgel can be or include a wet gel in which the polymer changes haveundergone toughening or hardening via an increased degree ofcross-linking.

The wet gel can be dried at a pressure of less than the criticalpressure of the liquid within the pores or voids of the wet gel. Forexample, if the wet gel includes water within the pores or voids thereofthe pressure of the wet gel during drying can remain below the criticalpressure of water. The wet gel, regardless of the particular liquidwithin the pores or voids of the wet gel can be subjected to a pressurethat remains below the critical pressure (about 7.38 MPa) of carbondioxide during drying. The wet gel can be dried at a pressure of lessthan 5,000 kPa, less than 4,000 kPa, less than 3,000 kPa, less than2,000 kPa, less than 1,000 kPa, less than 900 kPa, less than 800 kPa,less than 700 kPa, less than 600 kPa, less than 500 kPa, less than 400kPa, less than 300 kPa, less than 200 kPa, less than 150 kPa, less than125 kPa, or less than 100 kPa. In at least one example, the wet gel canbe dried at atmospheric pressure. In at least one other example, the wetgel can be dried at a pressure of less than atmospheric pressure. Forexample, the wet gel can be dried at a pressure of about 100 kPa, about95 kPa, about 90 kPa, about 80 kPa, about 70 kPa, about 60 kPa, about 50kPa, about 50 kPa, or less.

The wet gel can be dried by heating the wet gel to an elevatedtemperature from a low of about 5° C., about 10° C., about 15° C., about20° C., or about 25° C., to a high of about 80° C., about 90° C., about100° C., about 150° C., about 200° C., or about 300° C. For example, thewet gel can be heated to a temperature of about 5° C. to about 300° C.,about 10° C. to about 200° C., about 15° C. to about 150° C., or about25° C. to about 100° C. to produce the dried gel. In another example,the wet gel can be heated to a temperature of greater than 25° C. andless than 300° C., less than 250° C., less than 200° C., less than 150°C., less than 100° C., or less than 50° C. to produce the dried gel. Inanother example, the wet gel can be heated to a temperature of about 5°C. to about 300° C. while at atmospheric pressure or a pressure of lessthan 250 kPa, less than 200 kPa, less than 150 kPa, or less than 125 kPato produce the dried gel.

When heating the wet gel to produce the dried gel, the wet gel can beheated to the elevated temperature at a rate from a low of about 0.01°C./min, about 0.5° C./min, about 1° C./min, or about 2° C./min, to ahigh of about 10° C./min, about 15° C./min, about 25° C./min, or about50° C./min. For example, the wet gel can be heated to the elevatedtemperature at a rate of about 0.5° C./min to about 50° C./min, about 1°C./min to about 25° C./min, about 2° C./min to about 15° C./min, orabout 3° C./min to about 10° C./min. In another example, the wet gel canbe placed directly into a furnace or other heating device providing anenvironment already at the elevated temperature. In another example, thewet gel can be exposed to microwaves and/or any other energy source thatcan rapidly heat the wet gel to produce the dried gel. As such, thetemperature of the wet gel can be increased at a near infinite heatingrate. Accordingly, the temperature of the wet gel can be increased atany desired rate.

The wet gel can be heated at the elevated temperature for a period oftime from a low of about 0.01 hours, about 0.5 hours, about 1 hour,about 2 hours, or about 3 hours to a high of about 24 hours, about 48hours, about 72 hours, about 144 hours, about 288 hours, or more toproduce the dried gel. For example, the wet gel can be heated to theelevated temperature for a period of time of about 0.5 hours to about 72hours, about 1 hour to about 48 hours, about 2 hours to about 24 hours,about 3 hours to about 12 hours, or about 4 hours to about 6 hours toproduce the dried gel. In another example, the wet gel can be heated tothe elevated temperature for a period of time from about 1 hour to lessthan 288 hours, less than 144 hours, less than 72 hours, or less than 48hours to produce the dried gel. In another example, the wet gel can beheated to the elevated temperature for a period of time of at least 0.01hours, at least 0.5 hours, at least 1 hour, at least 2 hours, or atleast 3 hours and less than 288 hours to produce the dried gel.

The wet gel can be heated in any desired atmosphere. For example, thewet gel can be heated in an inert gas atmosphere. In another example,the wet gel can be heated in a reactive gas atmosphere. Illustrativeinert gases can include, but are not limited to, nitrogen, argon,helium, or any mixture thereof. Illustrative reactive gases can include,but are not limited to, ammonia, hydrogen fluoride, hydrogen chloride,or any mixture thereof. In another example, the wet gel can be heated inair, oxygen-rich air (greater than 21% of oxygen), or oxygen-lean air(21% or less of oxygen). Other suitable gases can include, but are notlimited to, carbon dioxide, methane, or a mixture thereof.

It should be noted that the wet gel can be converted or otherwise madeinto the dried gel under any combination of temperature, pressure,atmosphere, temperature rate increase, pressure rate decrease and/orincrease. For example, the wet gel can be heated under a vacuum in amicrowave. In another example, the wet gel can be heated at atmosphericpressure in a furnace. In another example the wet gel can be heated atatmospheric pressure or a pressure greater than atmospheric pressure ina furnace, a microwave, or other heating device.

The process used to dry the wet gel can be free of any solvent exchange.Said another way, the liquid within the pores or voids of the wet gelcan be removed without first replacing the liquid with a differentliquid. One conventional drying process can include replacing waterwithin the pores or voids of a wet gel with an organic solvent, e.g.,acetone, than water. The wet gels discussed and described herein can bedried without undergoing any exchange of liquid, which is often referredto as “solvent exchange.”

The dried gel can have a pore volume from a low of about 0.03 cm³/g,about 0.05 cm³/g, about 0.1 cm³/g, about 0.3 cm³/g, or about 0.5 cm³/gto a high of about 1 cm³/g, about 1.5 cm³/g, about 2 cm³/g, or about 2.5cm³/g. For example, the dried gel can have a pore volume of at least 0.1cm³/g, at least 0.2 cm³/g, at least 0.25 cm³/g, at least 0.3 cm³/g, atleast 0.35 cm³/g, at least 0.4 cm³/g, at least 0.45 cm³/g, at least 0.5cm³/g, at least 0.55 cm³/g, 0.6 cm³/g, at least 0.65 cm³/g, at least 0.7cm³/g, at least 0.75 cm³/g, or at least 0.8 cm³/g to a high of about 0.9cm³/g, about 0.95 cm³/g, about 1 cm³/g, about 1.05 cm³/g, about 1.1cm³/g, about 1.15 cm³/g, about 1.2 cm³/g, about 1.25 cm³/g, about 1.3cm³/g, about 1.35 cm³/g, about 1.4 cm³/g, about 1.45 cm³/g, about 1.5cm³/g, about 1.6 cm³/g, about 1.7 cm³/g, about 1.8 cm³/g, about 1.9cm³/g, about 2 cm³/g, about 2.1 cm³/g, about 2.2 cm³/g, about 2.3 cm³/g,about 2.4 cm³/g, or about 2.5 cm³/g. In another example, the dried gelcan have a pore volume from about 0.2 cm³/g to about 2 cm³/g, about 0.4cm³/g to about 1.8 cm³/g, about 0.6 cm³/g to about 1.4 cm³/g, about 1cm³/g to about 1.9 cm³/g, or about 0.3 cm³/g to about 1.7 cm³/g. Thepore volume of the dried gel activation can be measured using thenitrogen sorption technique as commonly known in the art.

The dried gel can have a pore size from a low of about 1 nm, about 1.5nm, about 2 nm, about 5 nm, about 10 nm, about 15 nm, about 20 nm, about25 nm, about 30 nm, about 25 nm, about 40 nm, about 45 nm, about 50 nm,about 51 nm, about 52 nm, about 53 nm, about 54 nm, or about 55 nm to ahigh of about 80 nm, about 90 nm, about 100 nm, about 110 nm, about 120nm, about 130 nm, about 140 nm, about 150 nm, about 200 nm, about 250nm, about 300 nm, about 350 nm, about 400 nm, about 450 nm, or about 500nm. For example, the dried gel can have a pore size of at least 10 nm,at least 20 nm, at least 30 nm, at least 40 nm, at least 50 nm, at least55 nm, or at least 60 nm to a high of about 80 nm, about 90 nm, about100 nm, about 110 nm, about 120 nm, about 130 nm, about 140 nm, about150 nm, about 200 nm, about 250 nm, about 300 nm, about 350 nm, about400 nm, about 450 nm, or about 500 nm. In another example, the dried gelcan have a pore size from about 1.5 nm to about 150 nm, about 10 nm toabout 80 nm, about 30 nm to about 90 nm, about 80 nm to about 100 nm.The pore size of the dried gel can be measured according to theBarret-Joyner-Halenda or “BJH” technique (described in E. P. Barret, L.G. Joyner, and P. P. Halenda, J. Amer. Chem. Soc., 73, 373 (1951)). Thepore size of the dried gel can also be measured according to the densityfunctional theory or “DFT” technique (described in Advances in Colloidand Interface Science, Volumes 76-77, July 1998, pp. 203-226, by P. I.Ravikovitch, G. L. Haller, and A. V. Neimark and C. Lastoski, K. E.Gubbins, and N. Quirke, J. Phys. Chem., 1993, 97 (18), pp. 4786-4796).The pore size referred to herein, unless otherwise noted, is the peak ofthe pore size distribution curve.

The dried gel can have a specific surface area from a low of about 5m²/g, about 10 m²/g, about 25 m²/g, about 50 m²/g, about 100 m²/g, about200 m²/g, about 300 m²/g, about 400 m²/g, about 500 m²/g, or about 600m²/g to a high of about 700 m²/g, about 800 m²/g, about 900 m²/g, about1,000 m²/g, about 1,100 m²/g, about 1,200 m²/g, about 1,300 m²/g, about1,400 m²/g, or about 1,500 m²/g. For example, the dried gel can have aspecific surface area of at least 5 m²/g, at least 20 m²/g, at least 30m²/g, at least 40 m²/g, or at least 50 m²/g to a high of about 100 m²/g,about 400 m²/g, about 700 m²/g, or about 1000 m²/g. In another example,the dried gel can have a specific surface area from about 20 m²/g toabout 700 m²/g, about 20 m²/g to about 400 m²/g, about 40 m²/g to about90 m²/g, about 50 m²/g to about 100 m²/g, or about 60 m²/g to about 400m²/g. The surface area of the dried gel refers to the total specificsurface area of the dried gel measured according to theBrunauer-Emmett-Teller or “BET” technique (described in S. Brunauer, P.H. Emmett, and E. Teller, J. Amer. Chem. Soc., 60, 309 (1938)). The BETtechnique employs an inert gas, for example nitrogen, to measure theamount of gas adsorbed on a material and is commonly used in the art todetermine the accessible surface area of materials.

The dried gel can have a pore size of about 10 nm to about 100 nm and apore volume of about 0.2 cm³/g to about 2 cm³/g. For example, the driedgel can have a pore size of about 60 nm to about 120 nm, about 10 nm toabout 80 nm, or about 80 nm to about 100 nm and a pore volume of about0.3 cm³/g to about 1.8 cm³/g, about 0.2 cm³/g to about 2 cm³/g, or about0.25 cm³/g to about 1.5 cm³/g. In another example, the dried gel canhave pore size of at least 10 nm, at least 30 nm, at least 50 nm, or atleast 60 nm to a high of about 80 nm, about 100 nm, about 125 nm, orabout 150 nm and a pore volume of at least 0.4 cm³/g, at least 0.5cm³/g, at least 0.6 cm³/g, or at least 0.7 cm³/g to a high of about 1cm³/g, about 1.2 cm³/g, about 1.5 cm³/g, about 1.8 cm³/g, or about 2cm³/g.

The dried gel can have a pore size of about 10 nm to about 100 nm and aspecific surface area of about 5 m²/g to about 1,500 m²/g. For example,the dried gel can have a pore size of about 60 nm to about 120 nm, about10 nm to about 80 nm, or about 80 nm to about 100 nm and a specificsurface area of about 20 m²/g to about 600 m²/g, about 20 m²/g to about400 m²/g, or about 60 m²/g to about 450 m²/g. In another example, thedried gel can have pore size of at least 10 nm, at least 30 nm, at least50 nm, or at least 60 nm to a high of about 80 nm, about 100 nm, about125 nm, or about 150 nm and a specific surface area of at least 5 m²/g,at least 10 m²/g, at least 15 m²/g, at least 20 m²/g, at least 40 m²/g,or at least 50, or at least 60 m²/g to a high of about 350 m²/g, about400 m²/g, about 500 m²/g, about 600 m²/g, about 700 m²/g, or about 1000m²/g.

The dried gel can have a specific surface area of about 5 m²/g to about1,500 m²/g and a pore volume of about 0.2 cm³/g to about 2 cm³/g. Forexample, the dried gel can have a specific surface area of about 20 m²/gto about 600 m²/g, about 20 m²/g to about 400 m²/g, or about 60 m²/g toabout 450 m²/g and a pore volume of about 0.3 cm³/g to about 1.8 cm³/g,about 0.2 cm³/g to about 2 cm³/g, or about 0.25 cm³/g to about 1.5cm³/g. In another example, the dried gel can have a specific surfacearea of at least 5 m²/g, at least 20 m²/g, at least 40 m²/g, or at least50 m²/g, or at least 60 m²/g to a high of about 100 m²/g, about 400m²/g, about 500 m²/g, about 600 m²/g, about 700 m²/g, or about 1000 m²/gand a pore volume of at least 0.4 cm³/g, at least 0.5 cm³/g, at least0.6 cm³/g, or at least 0.7 cm³/g to a high of about 1 cm³/g, about 1.2cm³/g, about 1.5 cm³/g, about 1.8 cm³/g, or about 2 cm³/g.

The dried gel can have a pore size of about 10 nm to about 100 nm, aspecific surface area of about 5 m²/g to about 1,500 m²/g, and a porevolume of about 0.2 cm³/g to about 2 cm³/g. For example, the dried gelcan have a pore size of about 60 nm to about 120 nm, about 10 nm toabout 80 nm, or about 80 nm to about 100 nm, a specific surface area ofabout 20 m²/g to about 600 m²/g, about 20 m²/g to about 400 m²/g, orabout 60 m²/g to about 450 m²/g and a pore volume of about 0.3 cm³/g toabout 1.8 cm³/g, about 0.2 cm³/g to about 2 cm³/g, or about 0.25 cm³/gto about 1.5 cm³/g. In another example, the dried gel can have pore sizeof at least 10 nm, at least 30 nm, at least 50 nm, or at least 60 nm toa high of about 80 nm, about 100 nm, about 125 nm, or about 150 nm, aspecific surface area of at least 5 m²/g, at least 20 m²/g, at least 40m²/g, or at least 50 m²/g, or at least 60 m²/g to a high of about 100m²/g, about 400 m²/g, about 500 m²/g, about 600 m²/g, about 700 m²/g, orabout 1000 m²/g, and a pore volume of at least 0.4 cm³/g, at least 0.5cm³/g, at least 0.6 cm³/g, or at least 0.7 cm³/g to a high of about 1cm³/g, about 1.2 cm³/g, about 1.5 cm³/g, about 1.8 cm³/g, or about 2cm³/g.

The dried gel can be used as is or the dried gel can be subjected to acarbonization or pyrolysis process to remove at least a portion of thenon-carbon components, e.g., hydrogen, oxygen, nitrogen, and othernon-carbon atoms, from the dried particles. The resulting carbonized orpyrolized product contains carbon and can be referred to as a pyrolizedcarbon product. Any pyrolysis process can be used. In one example, thedried gel can be placed into a rotary kiln and heated therein. Thepyrolysis process can be carried out under an inert atmosphere, e.g., anitrogen, argon, or other inert gas or gas mixture. The inert gas or gasmixture can be any gas or mixture of gases that do not react with thewet gel or the dried gel when the wet gel and/or the dried gel is heatedin the presence thereof. Pyrolysis processes are well known to those ofskill in the art. Suitable pyrolysis processes can include thosediscussed and described in U.S. Pat. Nos. 4,873,218; 4,997,804;5,124,364; and 5,556,892.

The duration of the pyrolysis, e.g., the period of time during which thedried gel is maintained at the elevated temperature can range from a lowof about 30 seconds, about 1 minute, about 5 minutes, about 10 minutes,about 20 minutes, or about 30 minutes to a high of about 1 hour, about 2hours, about 3 hours, about 5 hours, about 7 hours, about 20 hours, orlonger. The dried gel can by pyrolized by heating the dried gel to atemperature from a low of about 500° C., about 600° C., about 700° C.,about 800° C., about 900° C., or about 1,000° C. to a high of about1,500° C., about 1,700° C., about 1,900° C., about 2,100° C., about2,300° C. or about 2,400° C. For example, the pyrolysis dwelltemperature can be from about 500° C. to about 2,400° C., about 600° C.to about 1,800° C., about 600° C. to about 1,200° C., or about 650° C.to about 1,100° C.

It should be noted that if a pyrolized carbon product is desired, thewet gel can be heated directly to the pyrolysis temperature. Forexample, a wet gel can be placed into a furnace, oven, or other heatingdevice and can be heated from room temperature (e.g., about 25° C.) to apyrolysis temperature from about 500° C. to about 2,400° C. for thedesired time to produce the pyrolized carbon product. The temperatureramp rate can be the same or similar to the temperature ramp rate usedto produce the dried gel including direct placement of the wet gel intoa furnace or other environment already heated to the elevatedtemperature.

The pyrolized carbon product can be activated and such product can bereferred to as an activated carbon product. Alternatively, the wet gel,the dried gel, and/or the pyrolized carbon product can be activated toproduce the activated carbon product. Activating the wet gel, the driedgel, and/or the pyrolized carbon product can include any activationprocess or combination of activation processes known to those skilled inthe art. The activation time and/or activation temperature can affectthe performance of the resulting activated carbon material, as well asthe manufacturing cost thereof. For example, increasing the activationtemperature and the activation dwell time can yield a higher orincreased activation percentage of the pyrolized carbon product, but canalso correspond to the removal of more material compared to lowertemperatures and shorter dwell times. As such, higher activation canincrease performance of the final activated carbon, but it can alsoincrease the cost of the process by reducing the overall carbonizedproduct.

Pyrolized particles (or monolithic structures) can be activated bycontacting the pyrolized carbon product with an activating agent toproduce an activated product or activated carbon product. Illustrativeactivating agents can be or include gases such as carbon monoxide,carbon dioxide, steam, oxygen, or any combination or mixture thereof.Other activating agents can include other compounds or chemicals.

The activation process can range from about 1 minute to about 2 days,about 5 minutes to about 1 day, about 1 minute to about 18 hours, about1 minute to about 12 hours, about 5 minutes to about 8 hours, about 1minute to about 10 minutes, or about 1 hour to about 5 hours.

In one example of an activation process, the pyrolized particles can beweighed and placed in a rotary kiln and an automated gas controlmanifold and controller can be set to ramp rate of about 20° C. perminute. Carbon dioxide can be introduced to the kiln environment for aperiod of time once the proper activation temperature has been reached.After activation has occurred, the carbon dioxide can be replaced bynitrogen and the kiln can be cooled down. The recovered activatedparticles can be weighed at the end of the process to assess the levelof activation. Other activation processes are well known to those ofskill in the art. The activation temperature can range from a low ofabout 700° C., about 800° C., about 850° C., or about 900° C. to a highof about 1,100° C., about 1,200° C., about 1,300° C., or about 1,500° C.For example, the activation temperature can range from about 800° C. toabout 1,300° C., about 900° C. to about 1,050° C., or about 900° C. toabout 1,000° C. One skilled in the art will recognize that otheractivation temperatures, either lower or higher, may be employed. In oneor more embodiments, the wet gel, the dried gel, and/or the pyrolizedparticle can be activated by heating to a temperature of about 500° C.to about 1,300° C. in an atmosphere that includes carbon dioxide, carbonmonoxide, steam, oxygen, or any combination or any mixture thereof toproduce the activated carbon product.

The degree of activation can be measured in terms of the mass percent ofthe pyrolized particles that is lost during the activation step. Thedegree of activation can range anywhere from a low of about 1%, about5%, about 10%, about 20%, about 30%, about 40%, or about 50% to a highof about 60%, about 70%, about 80%, about 90%, about 95%, or about 99%.

The pore volume, pore size, and specific surface area of the pyrolizedcarbon product and the activated carbon product can be measured with thesame techniques used to measure the dried gel. The pyrolized and/or theactivated carbon product can have a pore volume from a low of about 0.03cm³/g, about 0.05 cm³/g, about 0.1 cm³/g, about 0.3 cm³/g, or about 0.5cm³/g to a high of about 1 cm³/g, about 1.5 cm³/g, about 2 cm³/g, orabout 2.5 cm³/g. For example, the pyrolized and/or the activated carbonproduct can have a pore volume of at least 0.1 cm³/g, at least 0.2cm³/g, at least 0.25 cm³/g, at least 0.3 cm³/g, at least 0.35 cm³/g, atleast 0.4 cm³/g, at least 0.45 cm³/g, at least 0.5 cm³/g, at least 0.55cm³/g, 0.6 cm³/g, at least 0.65 cm³/g, at least 0.7 cm³/g, at least 0.75cm³/g, or at least 0.8 cm³/g to a high of about 0.9 cm³/g, about 0.95cm³/g, about 1 cm³/g, about 1.05 cm³/g, about 1.1 cm³/g, about 1.15cm³/g, about 1.2 cm³/g, about 1.25 cm³/g, about 1.3 cm³/g, about 1.35cm³/g, about 1.4 cm³/g, about 1.45 cm³/g, about 1.5 cm³/g, about 1.6cm³/g, about 1.7 cm³/g, about 1.8 cm³/g, about 1.9 cm³/g, about 2 cm³/g,about 2.1 cm³/g, about 2.2 cm³/g, about 2.3 cm³/g, about 2.4 cm³/g, orabout 2.5 cm³/g. In another example, the pyrolized and/or the activatedcarbon product can have a pore volume from about 0.2 cm³/g to about 2cm³/g, about 0.4 cm³/g to about 1.8 cm³/g, about 0.6 cm³/g to about 1.4cm³/g, about 1 cm³/g to about 1.9 cm³/g, or about 0.3 cm³/g to about 1.7cm³/g.

The pyrolized and/or the activated carbon product can have a pore sizefrom a low of about 1 nm, about 1.5 nm, about 2 nm, about 5 nm, about 10nm, about 15 nm, about 20 nm, about 25 nm, about 30 nm, about 25 nm,about 40 nm, about 45 nm, about 50 nm, about 51 nm, about 52 nm, about53 nm, about 54 nm, or about 55 nm to a high of about 80 nm, about 90nm, about 100 nm, about 110 nm, about 120 nm, about 130 nm, about 140nm, about 150 nm, about 200 nm, about 250 nm, about 300 nm, about 350nm, about 400 nm, about 450 nm, or about 500 nm. For example, thepyrolized and/or the activated carbon product can have a pore size of atleast 10 nm, at least 20 nm, at least 30 nm, at least 40 nm, at least 50nm, at least 55 nm, or at least 60 nm to a high of about 80 nm, about 90nm, about 100 nm, about 110 nm, about 120 nm, about 130 nm, about 140nm, about 150 nm, about 200 nm, about 250 nm, about 300 nm, about 350nm, about 400 nm, about 450 nm, or about 500 nm. In another example, thepyrolized and/or the activated carbon product can have a pore size fromabout 1.5 nm to about 150 nm, about 10 nm to about 80 nm, about 30 nm toabout 90 nm, about 80 nm to about 100 nm.

The pyrolized and/or the activated carbon product can have a specificsurface area from a low of about 5 m²/g, about 10 m²/g, about 25 m²/g,about 50 m²/g, about 100 m²/g, about 200 m²/g, about 300 m²/g, about 400m²/g, about 500 m²/g, or about 600 m²/g to a high of about 700 m²/g,about 800 m²/g, about 900 m²/g, about 1,000 m²/g, about 1,100 m²/g,about 1,200 m²/g, about 1,300 m²/g, about 1,400 m²/g, or about 1,500m²/g. For example, the pyrolized and/or the activated carbon product canhave a specific surface area of at least 150 m²/g, at least 200 m²/g, atleast 250 m²/g, at least 300 m²/g, or at least 350 m²/g to a high ofabout 750 m²/g, about 850 m²/g, about 1,050 m²/g, or about 1,250 m²/g.In another example, the pyrolized and/or the activated carbon productcan have a specific surface area from about 200 m²/g to about 1,000m²/g, about 200 m²/g to about 800 m²/g, about 300 m²/g to about 550m²/g, about 350 m²/g to about 600 m²/g, or about 400 m²/g to about 850m²/g.

The pyrolized and/or the activated carbon product can have a pore sizeof about 10 nm to about 100 nm and a pore volume of about 0.2 cm³/g toabout 2 cm³/g. For example, the pyrolized and/or the activated carbonproduct can have a pore size of about 60 nm to about 120 nm, about 10 nmto about 80 nm, or about 80 nm to about 100 nm and a pore volume ofabout 0.3 cm³/g to about 1.8 cm³/g, about 0.2 cm³/g to about 2 cm³/g, orabout 0.25 cm³/g to about 1.5 cm³/g. In another example, the pyrolizedand/or the activated carbon product can have pore size of at least 10nm, at least 30 nm, at least 50 nm, or at least 60 nm to a high of about80 nm, about 100 nm, about 125 nm, or about 150 nm and a pore volume ofat least 0.4 cm³/g, at least 0.5 cm³/g, at least 0.6 cm³/g, or at least0.7 cm³/g to a high of about 1 cm³/g, about 1.2 cm³/g, about 1.5 cm³/g,about 1.8 cm³/g, or about 2 cm³/g.

The pyrolized and/or the activated carbon product can have a pore sizeof about 10 nm to about 100 nm and a specific surface area of about 5m²/g to about 1,500 m²/g. For example, the pyrolized and/or theactivated carbon product can have a pore size of about 60 nm to about120 nm, about 10 nm to about 80 nm, or about 80 nm to about 100 nm and aspecific surface area of about 200 m²/g to about 1,000 m²/g, about 200m²/g to about 800 m²/g, or about 400 m²/g to about 900 m²/g. In anotherexample, the pyrolized and/or the activated carbon product can have poresize of at least 10 nm, at least 30 nm, at least 50 nm, or at least 60nm to a high of about 80 nm, about 100 nm, about 125 nm, or about 150 nmand a specific surface area of at least 50 m²/g, at least 100 m²/g, atleast 150 m²/g, at least 200 m²/g, at least 300 m²/g, at least 350 m²/g,or at least 400 m²/g to a high of about 750 m²/g, about 800 m²/g, about900 m²/g, about 1,000 m²/g, about 1,100 m²/g, or about 1,250 m²/g.

The pyrolized and/or the activated carbon product can have a specificsurface area of about 5 m²/g to about 1,500 m²/g and a pore volume ofabout 0.2 cm³/g to about 2 cm³/g. For example, the pyrolized and/or theactivated carbon product can have a specific surface area of about 200m²/g to about 1,000 m²/g, about 200 m²/g to about 800 m²/g, or about 400m²/g to about 900 m²/g and a pore volume of about 0.3 cm³/g to about 1.8cm³/g, about 0.2 cm³/g to about 2 cm³/g, or about 0.25 cm³/g to about1.5 cm³/g. In another example, the pyrolized and/or the activated carbonproduct can have a specific surface area of at least 150 m²/g, at least200 m²/g, at least 300 m²/g, at least 350 m²/g, or at least 400 m²/g toa high of about 750 m²/g, about 800 m²/g, about 900 m²/g, about 1,000m²/g, about 1,100 m²/g, or about 1,250 m²/g and a pore volume of atleast 0.4 cm³/g, at least 0.5 cm³/g, at least 0.6 cm³/g, or at least 0.7cm³/g to a high of about 1 cm³/g, about 1.2 cm³/g, about 1.5 cm³/g,about 1.8 cm³/g, or about 2 cm³/g.

The pyrolized and/or the activated carbon product can have a pore sizeof about 10 nm to about 100 nm, a specific surface area of about 5 m²/gto about 1,500 m²/g, and a pore volume of about 0.2 cm³/g to about 2cm³/g. For example, the pyrolized and/or the activated carbon productcan have a pore size of about 60 nm to about 120 nm, about 10 nm toabout 80 nm, or about 80 nm to about 100 nm, a specific surface area ofabout 200 m²/g to about 1,000 m²/g, about 200 m²/g to about 800 m²/g, orabout 400 m²/g to about 900 m²/g, and a pore volume of about 0.3 cm³/gto about 1.8 cm³/g, about 0.2 cm³/g to about 2 cm³/g, or about 0.25cm³/g to about 1.5 cm³/g. In another example, the pyrolized and/or theactivated carbon product can have pore size of at least 10 nm, at least30 nm, at least 50 nm, or at least 60 nm to a high of about 80 nm, about100 nm, about 125 nm, or about 150 nm, a specific surface area of atleast 150 m²/g, at least 200 m²/g, at least 300 m²/g, at least 350 m²/g,or at least 400 m²/g to a high of about 750 m²/g, about 800 m²/g, about900 m²/g, about 1,000 m²/g, about 1,100 m²/g, or about 1,250 m²/g, and apore volume of at least 0.4 cm³/g, at least 0.5 cm³/g, at least 0.6cm³/g, or at least 0.7 cm³/g to a high of about 1 cm³/g, about 1.2cm³/g, about 1.5 cm³/g, about 1.8 cm³/g, or about 2 cm³/g.

In one or more embodiments, one or more modifier or composite materialscan be combined with the reaction mixture, the wet gel, the dried gel,and/or the pyrolized carbon product. As used herein, the terms“modifier” and “composite material” refer to any chemical element orcompound comprising a chemical element, or any combination of differentchemical elements and/or compounds that can modify one or moreproperties of the wet gel, the dried gel, and/or the pyrolized gel. Themodifier can change (increase or decrease) the resistance, capacity,power performance, composition, stability, and other properties of thewet gel, the dried gel, and/or the pyrolized gel. Examples of modifierswithin the context of the present disclosure can include, but are notlimited to, elements, and compounds or oxides comprising elements, ingroups 12-15 of the periodic table, other elements such as sulfur,tungsten and silver and combinations or mixtures thereof. For example,the modifier can include, but are not limited to, lead, tin, antimony,bismuth, arsenic, tungsten, silver, zinc, cadmium, indium, silicon,iron, sulfur, cobalt, nickel, bromine, chlorine, ruthenium, rhodium,platinum, palladium, zirconium, gold, oxides thereof, any alloysthereof, or any mixture thereof.

In at least one example, silicon in the form of a powder can be combinedwith the reaction mixtures to produce a wet gel containing silicondisposed or dispersed within the wet gel. The silicon powder can have anaverage particle size from a low of about 0.5 μm, about 1 μm, about 2μm, about 5 μm, or about 10 μm to a high of about 100 μm, about 500 μm,about 1,000 μm, about 2,500 μm, or about 5,000 μm. The silicon powdercan have a purity of about 95%, about 97%, about 99%, about 99.5%, about99.9%, about 99.99%, about 99.999%, or about 99.9999%.

The modifier can be present in the reaction mixture and/or the wet gelin an amount from a low of about 0.01 wt %, about 0.5 wt %, about 1 wt%, about 2 wt %, or about 3 wt % to a high of about 30 wt %, about 50 wt%, about 70 wt %, about 90 wt %, or about 95 wt %, based on the combinedweight of the hydroxybenzene compound, the aldehyde compound, theadditive, and the modifier in the reaction mixture. For example, themodifier can be present in the reaction mixture and/or the wet gel in anamount from about 0.01 wt % to about 90 wt %, about 1 wt % to about 70wt %, about 2 wt % to about 50 wt %, about 3 wt % to about 30 wt %, orabout 4 wt % to about 25 wt %, based on the combined weight of thehydroxybenzene compound, the aldehyde compound, the additive, and themodifier in the reaction mixture. Similarly, the modifier can be presentin the reaction mixture and/or the wet gel in an amount from a low ofabout 0.01 wt %, about 0.5 wt %, about 1 wt %, about 2 wt %, or about 3wt % to a high of about 30 wt %, about 50 wt %, about 70 wt %, about 90wt %, or about 95 wt %, based on the combined weight of the pyrolizedcarbon product or the activated carbon product and the modifier. Forexample, the modifier can be present in the pyrolized and/or activatedcarbon product in an amount from about 0.01 wt % to about 90 wt %, about1 wt % to about 70 wt %, about 2 wt % to about 50 wt %, about 3 wt % toabout 30 wt %, or about 4 wt % to about 25 wt %, based on the combinedweight of the pyrolized produce or the activated carbon product and themodifier.

In one or more embodiments, it may be desirable to produce wet gels anddried gels therefrom having little or no metal ions, e.g., silicon,sodium, iron, lithium, phosphorus, aluminum, arsenic, boron, orpotassium. Impurities such as metal atoms and/or metal ions can beintroduced to the polymer particles in gel form via any one or more ofseveral possible sources, which can include, but are not limited to, theparticular type of catalyst, leaching from the mixer and/or reactor intothe monomer component and/or during and/or after the polymer particlesin gel form are made. Accordingly, the materials used to make the mixer,line the inner surfaces or walls of the mixer, and/or componentsthereof, e.g., agitator blades, reactor, and the like can be chosen soas to reduce the potential or likelihood of contamination. For example,depending on a particular metal, the metal can leach or otherwise loosemetal ions that can be incorporated into the polymer particle in gelform during the suspension and/or emulsion polymerization thereof.

In one or more embodiments, the wet gel, the dried gel, the pyrolizedcarbon product, and/or the activated carbon product can have aconcentration of one or more metal atoms, one or more metal ions, or acombination of one or more metal atoms and one or more metal ions ofless than 1 wt %, less than 0.9 wt %, less than 0.8 wt %, less than 0.7wt %, less than 0.6 wt %, less than 0.5 wt %, less than 0.4 wt %, lessthan 0.3 wt %, less than 0.2 wt %, less than 0.15 wt %, less than 0.1 wt%, less than 0.7 wt %, less than 0.5 wt %, less than 0.3 wt %, less than0.1 wt %, less than 0.09 wt %, less than 0.07 wt %, less than 0.05 wt %,less than 0.03 wt %, less than 0.01 wt %, less than 0.009 wt %, lessthan 0.007 wt %, less than 0.005 wt %, less than 0.003 wt %, less than0.001 wt %, less than 0.0007 wt %, or less than 0.0005 wt %, based on atotal weight of the wet gel, the dried gel, and/or the pyrolized. Theconcentration of any metal atoms and/or metal ions present in the wetgel, the dried gel, the pyrolized carbon product, and the activatedcarbon product can be measured or determined by proton induced x-rayemission or “PIXE.” The metal atom(s) and/or metal ion(s) can be orinclude the elements having an atomic number from 11 to 92. The metalatom(s) and/or metal ion(s) can be or include elements having an atomicnumber of 3-5 and 11 to 92.

In one or more embodiments, the wet gel, the dried gel, the pyrolizedcarbon product, and/or the activated carbon product can contain lessthan 1,000 ppm, less than 700 ppm, less than 500 ppm, less than 300 ppm,less than 100 ppm, less than 75 ppm, less than 50 ppm, less than 25 ppm,less than 10 ppm, less than 5 ppm, or less than 1 ppm of any one or moreof the metal atoms (or metal ions) having an atomic number of 3 to 5and/or 11 to 92. For example, in one or more embodiments, the wet gel,the dried gel, the pyrolized carbon product, and/or the activated carbonproduct can contain less than 1,000 ppm, less than 700 ppm, less than500 ppm, less than 300 ppm, less than 100 ppm, less than 75 ppm, lessthan 50 ppm, less than 25 ppm, less than 10 ppm, less than 5 ppm, orless than 1 ppm sodium. In one or more embodiments, the wet gel, thedried gel, the pyrolized carbon product, and/or the activated carbonproduct can contain less than 1,000 ppm, less than 700 ppm, less than500 ppm, less than 300 ppm, less than 100 ppm, less than 75 ppm, lessthan 50 ppm, less than 25 ppm, less than 10 ppm, less than 5 ppm, orless than 1 ppm magnesium. In one or more embodiments, the wet gel, thedried gel, the pyrolized carbon product, and/or the activated carbonproduct can contain less than 1,000 ppm, less than 700 ppm, less than500 ppm, less than 300 ppm, less than 100 ppm, less than 75 ppm, lessthan 50 ppm, less than 25 ppm, less than 10 ppm, less than 5 ppm, orless than 1 ppm silicon. In one or more embodiments, the wet gel, thedried gel, the pyrolized carbon product, and/or the activated carbonproduct can contain less than 1,000 ppm, less than 700 ppm, less than500 ppm, less than 300 ppm, less than 100 ppm, less than 75 ppm, lessthan 50 ppm, less than 25 ppm, less than 10 ppm, less than 5 ppm, orless than 1 ppm sulfur. In one or more embodiments, the wet gel, thedried gel, the pyrolized carbon product, and/or the activated carbonproduct can contain less than 1,000 ppm, less than 700 ppm, less than500 ppm, less than 300 ppm, less than 100 ppm, less than 75 ppm, lessthan 50 ppm, less than 25 ppm, less than 10 ppm, less than 5 ppm, orless than 1 ppm calcium. In one or more embodiments, the wet gel, thedried gel, the pyrolized carbon product, and/or the activated carbonproduct can contain less than 1,000 ppm, less than 700 ppm, less than500 ppm, less than 300 ppm, less than 100 ppm, less than 75 ppm, lessthan 50 ppm, less than 25 ppm, less than 10 ppm, less than 5 ppm, orless than 1 ppm iron. In one or more embodiments, the wet gel, the driedgel, the pyrolized carbon product, and/or the activated carbon productcan contain less than 1,000 ppm, less than 700 ppm, less than 500 ppm,less than 300 ppm, less than 100 ppm, less than 75 ppm, less than 50ppm, less than 25 ppm, less than 10 ppm, less than 5 ppm, or less than 1ppm nickel. In one or more embodiments, the wet gel, the dried gel, thepyrolized carbon product, and/or the activated carbon product cancontain less than 1,000 ppm, less than 700 ppm, less than 500 ppm, lessthan 300 ppm, less than 100 ppm, less than 75 ppm, less than 50 ppm,less than 25 ppm, less than 10 ppm, less than 5 ppm, or less than 1 ppmcopper. In one or more embodiments, the wet gel, the dried gel, thepyrolized carbon product, and/or the activated carbon product cancontain less than 1,000 ppm, less than 700 ppm, less than 500 ppm, lessthan 300 ppm, less than 100 ppm, less than 75 ppm, less than 50 ppm,less than 25 ppm, less than 10 ppm, less than 5 ppm, or less than 1 ppmchromium. In one or more embodiments, the wet gel, the dried gel, thepyrolized carbon product, and/or the activated carbon product cancontain less than 1,000 ppm, less than 700 ppm, less than 500 ppm, lessthan 300 ppm, less than 100 ppm, less than 75 ppm, less than 50 ppm,less than 25 ppm, less than 10 ppm, less than 5 ppm, or less than 1 ppmzinc. In some embodiments other impurities such as hydrogen, oxygenand/or nitrogen can be present in levels ranging from less than 10%,less than 9%, less than 8%, less than 7%, less than 6%, less than 5%,less than 4%, less than 3%, less than 2%, less than 1%, less than 0.5%,less than 0.1%, less than 0.05%, or less than 0.01%.

One way to reduce and/or eliminate contamination of metal or metal ionswithin the wet gel, the dried, gel, and/or the pyrolized carbon productcan be to construct the mixer and/or reactor from non-reactive or verylow reactive materials, materials having a reduced tendency to leach orgive up metal atoms or ions to the reaction mixture as compared tomaterials that are known to leach metal atoms into the reaction mixture.Some potential materials that can be suitable for making the mixerand/or reactor used to produce the wet gel that can also help reduce thecontamination of metal ions leaching or otherwise transferring from themixer and/or reactor to the wet gel can include, but are not limited to,metals, glass, e.g., a glass lined vessel, fiber reinforced vessels,e.g., FRP (FRB, FRVE, FRSVE.) and Dual laminate like PP/FRP, PVC/FRP,CPVC/FRP, PVDF/FRP, ECTFE/FRP, ETFE/FRP, FEP/FRP and PFA/FRP, polymerreactors, e.g., Teflon, polyethylene (PE), polypropylene (PP),Chlorinated Poly(Vinyl Chloride) (CPVC). Illustrative metals caninclude, but are not limited to, cobalt, chromium, tungsten, carbon,silicon, iron, manganese, molybdenum, vanadium, nickel, boron,phosphorous, sulfur, titanium, aluminum, copper, tungsten, alloysthereof, or any combination or mixture thereof. For example, the one ormore inner surfaces of the reactor can be made of steel such asstainless steels, carbon steels, tool steels, alloy steels, or anycombination or mixture thereof. Illustrative steels can include, but arenot limited to, A387 Grade 11 low chrome steel, 304 stainless steel, 316stainless steel, and 347 stainless steel.

In one or more embodiments, the surfaces of the mixer and/or reactorand/or components thereof can be treated to reduce the likelihood ofmetal ions (or other impurities) from leaching or otherwise transferringfrom the surfaces to the wet gel. The inner metal surfaces can besubjected a passivation process to reduce the likelihood ofcontamination of the wet gel with metal ions. For example, metalsurfaces of the mixer and/or reactor that contact the suspension and/oremulsion can be subjected one or more treatment processes such ascarburization, boronization, and/or nitridization. In another examplethe inner surfaces of the mixer and/or reactor can be subjected to apickling process. A pickling process can include treating a metal orother surface to remove one or more impurities, e.g., one or morestates, inorganic contaminants, rust or scale from ferrous, copper,and/or aluminum metals or alloys. The surface can be treated with asolution or “pickle liquor” that contains one or more acids, forexample. The one or more acids can be or include, but are not limitedto, hydrochloric acid, sulfuric acid, nitric acid, or any combination ormixture thereof.

In one or more embodiments, the mixer and/or reactor or inner surfacesthereof can be heated in the presence of a carbon source to atemperature below the melting point of the inner surfaces, butsufficiently high to cause carbon to deposit within the outer layer orsurface of the inner surfaces, e.g., the layer or surface exposed to thereaction mixture. Any suitable form of carbon can be used as the carbonsource, for example carbon containing gases, liquids, solids, and/orplasmas. Illustrative gases can include, but are not limited to, carbondioxide, methane, ethane, propane, or the like. In another example, themixer and/or reactor or/or inner surfaces thereof can be heated in thepresence of a boron source to a sufficient temperature, but below themelting point of the inner surfaces, but sufficiently high to causeboron to diffuse into the surface and form borides with the material. Inyet another example, the mixer and/or reactor and/or inner surfacesthereof can be heated in the presence of a nitrogen source to asufficient temperature, but below the melting point of the innersurfaces, causing nitrogen to diffuse into the surface and form nitrideswith the material. Any suitable process can be used to nitride the innersurfaces of the mixer and/or reactor and/or other components thereof.For example, gas nitriding, liquid or salt bath nitriding, and ion orplasma nitriding can be used. In another example, the mixer and/orreactor, and/or inner surfaces thereof can under-go both carburizationand nitridization (“carbonitriding”) in which both carbon and nitrogenare diffused into the inner surfaces thereof. Subjecting the mixerand/or reactor and/or other components and/or inner surfaces thereof tocarburization, boronization, and/or nitridization can reduce oreliminate the likelihood that metal ions or other contaminants from themixer and/or reactor and/or other components thereof can leach orotherwise transfer therefrom to the reaction mixture and/or the wet gel.

The particles after drying, after pyrolysis, and/or after activation canhave an average cross-sectional length of about 0.1 μm, about 1 μm,about 10 μm, about 50 μm, about 75 μm, about 0.1 mm or more, about 0.5mm or more, about 1 mm or more, about 1.5 mm or more, about 2 mm ormore, about 2.5 mm or more, about 3 mm or more, about 3.5 mm or more,about 4 mm or more, about 4.5 mm or more, about 5 mm or more, about 5.5mm or more, or about 6 mm or more. The particles after drying, afterpyrolysis, and/or after activation can have an average cross-sectionallength from a low of about 0.1 mm, about 0.5 mm, about 1 mm, about 1.5mm, about 2 mm, about 2.5 mm, about 3 mm, about 3.5 mm, or about 4 mm toa high of about 5 mm, about 7 mm, about 10 mm, about 12 mm, about 15 mm,about 18 mm, about 20 mm, about 25 mm, or about 30 mm. In one or moreembodiments, the particles after drying, after pyrolyzing, and/or afteractivation can have an average cross-sectional length from a low ofabout 1 μm, about 10 μm, about 50 μm, about 100 μm, about 200 μm, about300 μm, about 500 μm, about 700 μm, or about 1,000 μm to a high of about1.1 mm, about 1.3 mm, about 1.5 mm, about 2 mm, about 3 mm, about 4 mm,about 5 mm, about 7 mm, or about 10 mm.

If a modifier is used in making the wet gel, the modifier can beincorporated within the pore structure and/or on the surface of theparticles after drying, after pyrolysis, and/or after activation orincorporated in any number of other ways. For example, in someembodiments, the particles after drying, after pyrolysis, and/or afteractivation can include a coating of the modifier at least partially onthe surface thereof. In some embodiments, the particles after drying,after pyrolysis, and/or after activation can include greater than 100ppm of a modifier.

The properties of the particles after drying, after pyrolysis, and/orafter activation can be modified, at least in part, by the amount of themodifier in the particles after drying, after pyrolysis, and/or afteractivation. Accordingly, in some embodiments, the particles afterdrying, after pyrolysis, and/or after activation can include at least0.1%, at least 0.25%, at least 0.5%, at least 1%, at least 5%, at least10%, at least 25%, at least 50%, at least 75%, at least 90%, at least95%, at least 99% or at least 99.5% of the modifier. For example, insome embodiments, the particles after drying, after pyrolysis, and/orafter activation can include from about 0.5% and 99.5% carbon and fromabout 0.5% and 99.5% modifier. The percent of the modifier is calculatedon weight percent basis (wt %). In some other more specific embodiments,the modifier can be selected from iron, tin, silicon, nickel andmanganese.

The total ash content of the particles after drying, after pyrolysis,and/or after activation may, in some instances, can have an effect onthe performance of the particles after drying, after pyrolysis, and/orafter activation. Accordingly, in some embodiments, the ash content ofthe particles after drying, after pyrolysis, and/or after activation canbe from about 0.1% to about 0.001% weight percent ash. For example insome specific embodiments the ash content of the particles after drying,after pyrolysis, and/or after activation can be less than 0.1%, lessthan 0.08%, less than 0.05%, less than 0.03%, than 0.025%, less than0.01%, less than 0.0075%, less than 0.005% or less than 0.001%.

“Ash content” refers to the nonvolatile inorganic matter which remainsafter subjecting a substance to a high decomposition temperature.Herein, the ash content of a carbon material, e.g., the polymerparticles after drying, after pyrolysis, and/or after activation, can becalculated from the total PIXE impurity content as measured by protoninduced x-ray emission, assuming that nonvolatile elements arecompletely converted to expected combustion products (e.g., oxides).“Carbon material” refers to a material or substance composedsubstantially of carbon (e.g., greater than 90%, greater than 95%,greater than 99%, or greater than 99.9% carbon on a weight basis).Carbon materials include ultrapure as well as amorphous and crystallinecarbon materials. Examples of carbon materials can include, but are notlimited to, activated carbon, pyrolized dried polymer gels, pyrolizedpolymer cryogels, pyrolized polymer xerogels, pyrolized polymeraerogels, activated dried polymer gels, activated polymer cryogels,activated polymer xerogels, activated polymer aerogels, and the like.

Depending, at least in part, on the end use of the wet gel, the wet gelitself, the dried gel, the gel after pyrolizing, the gel afteractivation, or a combination of wet gel, dried gel, pyrolized carbonproduct, and/or activated carbon product can be used in one or moreapplications. Illustrative applications the wet gel, dried gel,pyrolized carbon product, and/or activated carbon product can be used incan include, but are not limited to, insulation, energy such as incapacitors, batteries, and fuel cells, medicine such as in drugdelivery, transportation such as in hydrogen or other fuel storage,sensors, sports, catalysts, hazardous waste water treatment, catalystsupports, sorbents, dielectrics, impedance matcher, detectors,filtrations, ion exchange, high-energy physics applications, wastemanagement, such as adsorption of waste fluids and/or waste gases, andthe like. As such, the wet gel, the dried gel, pyrolized carbon product,the activated carbon product, or a combination of the wet gel, the driedgel, the pyrolized carbon product, and/or the activated carbon productcan be used alone and/or as a component of a system, device, or otherstructure.

One end use for the wet gel, dried gel, pyrolized carbon product, and/oractivated carbon product can include incorporation of the dried gel intoand/or on a composite wood product. Illustrative composite wood productscan include, but are not limited to, particleboard, fiberboard such asmedium density fiberboard (“MDF”) and/or high density fiberboard(“HDF”), waferboard, oriented strand board plywood (“OSB”), plywood,laminated veneer lumber (“LVL”), laminated veneer boards (“LVB”),engineered wood flooring, and the like.

Another end use for the wet gel, dried gel, pyrolized carbon product,and/or activated carbon product can include incorporation of the driedgel into and/or on a fiberglass product. As used herein, the terms“fiber,” “fibrous,” “fiberglass,” “fiber glass,” “glass fibers,” and thelike are used interchangeably and refer to materials that have anelongated morphology exhibiting an aspect ratio (length to thickness) ofgreater than 100, generally greater than 500, and often greater than1000. Indeed, an aspect ratio of over 10,000 is possible. Suitablefibers can be glass fibers, natural fibers, synthetic fibers, mineralfibers, ceramic fibers, metal fibers, carbon fibers, or any combinationor mixture thereof. Illustrative glass fibers can include, but are notlimited to, A-type glass fibers, C-type glass fibers, E-type glassfibers, S-type glass fibers, ECR-type glass fibers, wool glass fibers,and any combination thereof. The term “natural fibers,” as used hereinrefers to plant fibers extracted from any part of a plant, including,but not limited to, the stem, seeds, leaves, roots, or phloem.Illustrative natural fibers can include, but are not limited to, cotton,jute, bamboo, ramie, bagasse, hemp, coir, linen, kenaf, sisal, flax,henequen, and any combination thereof. Illustrative synthetic fibers caninclude, but are not limited to, synthetic polymers, such as polyester,polyamide, aramid, and any combination thereof. In at least one specificembodiment, the fibers can be glass fibers that are wet use choppedstrand glass fibers (“WUCS”). Wet use chopped strand glass fibers can beformed by conventional processes known in the art. The WUCS can have amoisture content ranging from a low of about 5%, about 8%, or about 10%to a high of about 20%, about 25%, or about 30%.

Fiberglass products can be used by themselves or incorporated into avariety of products. For example, fiberglass products can be used as orincorporated into insulation batts or rolls, composite flooring, asphaltroofing shingles, siding, gypsum wall board, roving, microglass-basedsubstrate for printed circuit boards, battery separators, filter stock,tape stock, carpet backing, commercial and industrial insulation, and asreinforcement scrim in cementitious and non-cementitious coatings formasonry.

Incorporation of the wet gel, dried gel, pyrolized carbon product,and/or activated carbon product into and/or on a composite wood productand/or a fiberglass product can increase the thermal and/or acousticinsulation properties of the composite product. In one or moreembodiments, the wet gel, dried gel, pyrolized carbon product, and/oractivated carbon product can be adhered, glued, or otherwise affixed toone or more surfaces of a composite wood product or fiberglass productto provide a thermally and/or acoustically insulated product. In anotherexample, the wet gel, dried gel, pyrolized carbon product, and/oractivated carbon product can be sandwiched between two or more layers ofwood substrates or fiberglass to produce a product containing the wetgel, dried gel, pyrolized carbon product, and/or activated carbonproduct. For example, in the context of plywood, a layer of the wet gel,dried gel, pyrolized carbon product, and/or activated carbon product canbe sandwiched between two layers of veneer.

Any suitable adhesive can be used to bind the wet gel, dried gel,pyrolized carbon product, and/or activated carbon product to wood and/orfiberglass in making the product containing the dried gel. Illustrativeadhesives can include, but are not limited to, isocyanate resin,aldehyde based resins such as urea-formaldehyde, phenol formaldehyde,melamine formaldehyde, phenol-urea-formaldehyde resin,resorcinol-formaldehyde resin, phenol-resorcinol-formaldehyde resin, andmelamine-urea-formaldehyde resin, or any mixture thereof.

Incorporation of the wet gel, dried gel, pyrolized carbon product,and/or activated carbon product into and/or on a composite wood productand/or a fiberglass product can include affixing the wet gel, dried gel,pyrolized carbon product, and/or activated carbon product onto one ormore sheets or layers of material. Illustrative sheets of material caninclude, but are not limited to, paper sheets, polymer sheets,paper/polymer sheets, or any mixture thereof. In another example,incorporation of the wet gel, dried gel, pyrolized carbon product,and/or activated carbon product into and/or on a composite wood productand/or a fiberglass product can include applying a layer or covering ofmaterial that contains the dried gel. For example, wet gel, dried gel,pyrolized carbon product, and/or activated carbon product particles canbe sandwiched between two or more layers of the sheet of material. Thissandwiched layer having at least a first outer layer and a second outerlayer of the sheet material and a core layer of the wet gel, dried gel,pyrolized carbon product, and/or activated carbon product can be affixedto one or more outer surfaces of the composite wood product and/or thefiberglass product and/or incorporated into the composite wood productand/or the fiberglass product.

Another end use for the wet gel, dried gel, pyrolized carbon product,and/or activated carbon product can include incorporation of the driedgel into one or more liquids that can be used to coat a surface. Forexample, the wet gel, dried gel, pyrolized carbon product, and/oractivated carbon product can be incorporated into a paint to provide apaint containing the dried gel. The paint can then be applied to a wallor to an exterior and/or interior side of a roof or any other surface toprovide a coated surface containing the dried gel.

EXAMPLES

In order to provide a better understanding of the foregoing discussion,the following non-limiting examples are offered. Although the examplesmay be directed to specific embodiments, they are not to be viewed aslimiting the invention in any specific respect. All parts, proportions,and percentages are by weight unless otherwise indicated.

Example I

For all examples (Ex. 1-15), a phenol-formaldehyde prepolymer wasproduced according to the following procedure. About 520 grams of phenoland about 465 grams of formaldehyde (50 wt % aqueous solution) wereadded to a reactor and heated to a temperature of about 55° C. About 16grams of triethylamine was added to the reactor and the temperature ofthe mixture was increased to about 78° C. and reaction between thecomponents of the mixture was continued until a viscosity of 60centistokes was reached. The reaction mixture was cooled to about 55° C.and distilled to provide a water content of about 12%. The reactionmixture was further cooled to about 25° C. and named as prepolymer.

To the prepolymer the appropriate amounts of acetic acid, maleicanhydride, ethylene glycol, PEG-PPG-PEG copolymer, citric acid, and/orresorcinol were added to produce a reaction mixture. The amount of eachcomponent relative to one another in the reaction mixture is shown inTable 1 below. The reaction mixture was heated in a 10 liter glassreactor to about 85° C. for about 5 hours under agitation. The mixturewas cooled to about 55° C. and transferred to two 2.5 gallon containers.The containers were sealed and placed in a heated oven at 70° C. forabout 48 hours. The sealed containers were then heated to 90° C. forabout 24 hours and cooled to provide the wet gel product.

TABLE 1 Wet-Gel Composition PEG-PPG- Acetic Maleic Ethylene PEG CitricF:P Phenol, Form., Acid, Anhy., Glycol, Copolymer, Acid, Resorc., TEA,Water, Molar Ex. wt % wt % wt % wt % wt % wt % wt % wt % wt % wt % Ratio1 19.1 8.53 60.98 2.74 — 4.57 1.22 — 0.57 2.29 1.4:1 2 24.09 10.76 53.852.31 — 3.08 2.31 — 0.72 2.88 1.4:1 3 23.82 10.64 53.20 4.94 — 3.04 0.76— 0.71 3.60 1.4:1 4 27.72 12.38 53.10 2.65 — — — — 0.83 3.32 1.4:1 519.76 8.83 63.09 0.63 — 4.73 — — 0.59 2.37 1.4:1 6 20.47 9.14 65.36 0.65— — 1.31 — 0.61 2.46 1.4:1 7 36.21 16.17 34.68 5.20 — — 2.31 — 1.09 4.341.4:1 8 20.74 9.26 66.23 0.66 — — — — 0.62 2.49 1.4:1 9 20.01 8.94 63.902.88 — — 1.28 — 0.60 2.39 1.4:1 10 15.82 7.07 70.71 1.52 — 2.02 0.51 —0.47 1.88 1.4:1 11 18.79 8.39 30.00 5.00 10.00 10.00  10.00  5.00 0.562.25 2.5:1 12 18.47 8.25 68.74 1.77 — — — — 0.55 2.22 1.4:1 13 40.7118.19 30.00 5.00 — — — — 1.22 4.88 2.5:1 14 42.04 18.78 26.85 6.04 — — —— 1.26 5.03 1.4:1 15 31.32 13.99 30.00 — 10.00 10.00  — — 0.94 3.752.5:1

The wet gels were dried in an air atmosphere at a temperature of about200° C. for about 15 hours to produce dried gels. The specific surfacearea (SSA), pore volume (PV), and pore size (PSD) were measured for thedried gels in Examples 1-3 and 5-10. All of the dried gels in Examples1-15 were pyrolized under a nitrogen atmosphere at a temperature ofabout 900° C. for about 2 hours to produce a pyrolized or carbonproduct. The specific surface area (SSA), pore volume (PV), and poresize (PSD) were measured for the pyrolized carbon products in Examples1-15. The specific surface area (SSA), pore volume (PV), and pore size(PSD) for the dried gels and the pyrolized carbon products are shown inTable 2 below.

TABLE 2 Properties Pyrolized Carbon Product Properties Dried GelProperties SSA, PV, PSD, SSA, PV, PSD, Ex. m²/g cm³/g nm m²/g cm³/g nm 1473 1.38 90 145 0.72 50 2 424 0.93 30 167 0.77 25 3 496 0.91 48 167 0.9150 4 380 0.85 50 — — — 5 428 0.66 90 97 0.39 85 6 426 0.56 90 87 0.41 907 389 0.51 15 270 0.59 18 8 404 0.47 90 91 0.40 90 9 460 0.41 40 1000.31 90 10 485 0.41 90 47 0.16 90 11 318 0.39 20 — — — 12 488 0.39 35 —— — 13 335 0.38 25 — — — 14 342 0.36 15 — — — 15 142 0.1 80 — — —

As shown in Table 2 above, the physical properties of the dried gels andthe pyrolized carbon products could be adjusted or tailored based on theparticular composition of the reaction mixture. For example, under someconditions increasing acetic acid increased the pore size, pore volume,and specific surface area.

Example II

A wet gel was made and pyrolized to produce a pyrolized carbon productcomposed of carbon (Ex. 16). A prepolymer was made according to ExampleI above. To about 200 grams of the prepolymer, a mixture of about 6grams resorcinol, about 6 grams maleic anhydride, about 10 grams citricacid, about 10 grams poly(ethylene glycol)-poly(propyleneglycol)-poly(ethylene glycol) block polymer, about 50 grams acetic acid,and about 50 grams ethylene glycol was added. The mixture was placedinto a container, sealed, and heated in an oven at about 90° C. forabout 43 hours. The resulting wet gel was then placed in a tube furnaceand pyrolized under a nitrogen atmosphere at a temperature of about 900°C. for about 2 hours. The pore volume of the resulting pyrolized carbonproduct was about 0.25 cm³/g and the pore size distribution was about 20nm.

Example III

A wet gel containing silicon powder was made and pyrolized to produce apyrolized carbon product composed of silicon carbide (Ex. 17). Aprepolymer was made according to Example I above. To about 200 grams ofthe prepolymer, a mixture of about 6 grams resorcinol, about 6 gramsmaleic anhydride, about 10 grams citric acid, about 10 gramspoly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) blockpolymer, about 50 grams acetic acid, about 50 grams ethylene glycol, andabout 280 grams silicon powder was added. The mixture was then placedinto a container, sealed, and heated in an oven at a temperature ofabout 90° C. for about 43 hours. The resulting wet gel were then placedin a tube furnace and pyrolized under a nitrogen atmosphere at atemperature of about 1,050° C. for about 2 hours to produce a siliconcarbide gel. The pore volume of the silicon carbide product was about0.20 cm³/g and the pore size distribution was centered on about 50 nm.

Embodiments of the present disclosure further relate to any one or moreof the following paragraphs:

1. A method for making a wet gel, comprising: combining at least onehydroxybenzene compound, at least one aldehyde compound, and at leastone additive comprising a carboxylic acid, an anhydride, a homopolymer,a copolymer, or any mixture thereof to produce a reaction mixture; andreacting at least the hydroxybenzene compound and the aldehyde compoundto produce a wet gel, wherein the reaction mixture comprises about 10 wt% to about 65 wt % of the hydroxybenzene compound, about 5 wt % to about25 wt % of the aldehyde compound, up to about 85 wt % of the carboxylicacid, up to about 40 wt % of the anhydride, up to about 40 wt % of thehomopolymer, and up to about 40 wt % of the copolymer, wherein thereaction mixture comprises about 10 wt % to about 90 wt % of theadditive, and wherein all weight percent values are based on thecombined weight of the hydroxybenzene compound, the aldehyde compound,and the additive.

2. A method for making a dried gel, comprising: combining at least onesolvent, at least one hydroxybenzene compound, at least one aldehydecompound, and at least one additive comprising a carboxylic acid, ananhydride, a homopolymer, a copolymer, or any mixture thereof to producea reaction mixture; reacting at least the hydroxybenzene compound andthe aldehyde compound to produce a wet gel; and drying the wet gel toproduce a dried gel, wherein a pressure exerted on the wet gel duringdrying is maintained below a critical pressure of the solvent, andwherein the dried gel has at least one property selected from the groupconsisting of: an average pore size of about 10 nm to about 150 nm, aspecific surface area of about 5 m²/g to about 1,500 m²/g, and a porevolume of about 0.2 cm³/g to about 2.5 cm³/g.

3. A method for making a dried gel, comprising: determining one or moredesired properties of a dried gel selected from the group consisting of:an average pore size of about 10 nm to about 150 nm, a specific surfacearea of about 5 m²/g to about 1,500 m²/g, and a pore volume of about 0.2cm³/g to about 2.5 cm³/g; combining a solvent, at least onehydroxybenzene compound, at least one aldehyde compound, and at leastone additive comprising a carboxylic acid, an anhydride, a homopolymer,a copolymer, or any a mixture thereof to produce a reaction mixture;reacting at least the hydroxybenzene compound and the aldehyde compoundto produce a wet gel; and drying the wet gel to produce a dried gel,wherein a pressure exerted on the wet gel during drying is maintainedbelow a critical pressure of the solvent, and wherein the amount of thehydroxybenzene compound, the amount of the aldehyde compound, and theamount of the additive are controlled to produce the dried gel havingthe one or more desired properties.

4. A method for making a dried gel, comprising: reacting at least onehydroxybenzene compound and at least one aldehyde compound to produce awet gel; and drying the wet gel to produce a dried gel, wherein apressure exerted on the wet gel during drying is maintained below acritical pressure of the solvent, and wherein the dried gel has at leastone property selected from the group consisting of: an average pore sizeof about 10 nm to about 150 nm, a specific surface area of about 5 m²/gto about 1,500 m²/g, and a pore volume of about 0.2 cm³/g to about 2.5cm³/g.

5. A method for making a dried gel, comprising: reacting phenol andformaldehyde with one another to produce a wet gel; and drying the wetgel to produce a dried gel, wherein a pressure exerted on the wet gelduring drying is maintained below a critical pressure of the solvent,and wherein the dried gel has at least one property selected from thegroup consisting of: an average pore size of about 10 nm to about 150nm, a specific surface area of about 5 m²/g to about 1,500 m²/g, and apore volume of about 0.2 cm³/g to about 2.5 cm³/g.

6. The method according to any one of paragraphs 1 to 5, wherein thereaction mixture comprises about 15 wt % to about 90 wt % of theadditive, based on the combined weight of the hydroxybenzene compound,the aldehyde compound, and the additive.

7. The method according to any one of paragraphs 1 to 6, whereinreaction mixture comprises about 20 wt % to about 90 wt % of theadditive, based on the combined weight of the hydroxybenzene compound,the aldehyde compound, and the additive.

8. The method according to any one of paragraphs 1 to 7, whereinreaction mixture comprises about 25 wt % to about 90 wt % of theadditive, based on the combined weight of the hydroxybenzene compound,the aldehyde compound, and the additive.

9. The method according to any one of paragraphs 1 to 8, whereinreaction mixture comprises about 30 wt % to about 90 wt % of theadditive, based on the combined weight of the hydroxybenzene compound,the aldehyde compound, and the additive.

10. The method according to any one of paragraphs 1 to 9, whereinreaction mixture comprises about 35 wt % to about 90 wt % of theadditive, based on the combined weight of the hydroxybenzene compound,the aldehyde compound, and the additive.

11. The method according to any one of paragraphs 1 to 10, wherein thereaction mixture comprises about 20 wt % to about 75 wt % of thehydroxybenzene and the aldehyde compound, based on the combined weightof the hydroxybenzene compound, the aldehyde compound, and the additive.

12. The method according to any one of paragraphs 1 to 11, wherein thereaction mixture comprises about 25 wt % to about 70 wt % of thecarboxylic acid, based on the combined weight of the hydroxybenzenecompound, the aldehyde compound, and the additive.

13. The method according to any one of paragraphs 1 to 12, wherein thereaction mixture comprises about 30 wt % to about 65 wt % of thecarboxylic acid, based on the combined weight of the hydroxybenzenecompound, the aldehyde compound, and the additive.

14. The method according to any one of paragraphs 1 to 13, wherein thereaction mixture comprises about 0.5 wt % to about 10 wt % of theanhydride, based on the combined weight of the hydroxybenzene compound,the aldehyde compound, and the additive.

15. The method according to any one of paragraphs 1 to 14, wherein thereaction mixture comprises about 0.5 wt % to about 10 wt % of thehomopolymer, based on the combined weight of the hydroxybenzenecompound, the aldehyde compound, and the additive.

16. The method according to any one of paragraphs 1 to 15, wherein thereaction mixture comprises about 1 wt % to about 10 wt % of thecopolymer, based on the combined weight of the hydroxybenzene compound,the aldehyde compound, and the additive.

17. The method according to any one of paragraphs 1 to 16, wherein thereaction mixture comprises about 30 wt % to about 70 wt % of thecarboxylic acid, about 0.1 wt % to about 10 wt % of the anhydride, andabout 0.1 wt % to about 8 wt % of the copolymer, based on the combinedweight of the hydroxybenzene compound, the aldehyde compound, and theadditive.

18. The method according to any one of paragraphs 1 to 17, wherein thereaction mixture comprises about 30 wt % to about 70 wt % of thecarboxylic acid and about 0.1 wt % to about 8 wt % of the copolymer,based on the combined weight of the hydroxybenzene compound, thealdehyde compound, and the additive.

19. The method according to any one of paragraphs 1 to 18, wherein thereaction mixture comprises about 30 wt % to about 70 wt % of thecarboxylic acid and about 0.1 wt % to about 8 wt % of the anhydride,based on the combined weight of the hydroxybenzene compound, thealdehyde compound, and the additive.

20. The method according to any one of paragraphs 1 to 4 or 6 to 19,wherein the hydroxybenzene compound comprises phenol, resorcinol,cresol, catechol, hydroquinone, phloroglucinol, or any mixture thereof.

21. The method according to any one of paragraphs 1 to 4 or 6 to 20,wherein the aldehyde compound comprises formaldehyde, acetaldehyde,propionaldehyde, butyraldehyde, furfuraldehyde, glucose, benzaldehyde,cinnamaldehyde, or any mixture thereof.

22. The method according to any one of paragraphs 1 to 21, wherein theadditive comprises the carboxylic acid.

23. The method according to any one of paragraphs 1 to 22, wherein theadditive comprises the carboxylic acid, and wherein the carboxylic acidcomprises a monocarboxylic acid, a dicarboxylic acid, or a tricarboxylicacid.

24. The method according to any one of paragraphs 1 to 23, wherein theadditive comprises the carboxylic acid, and wherein the carboxylic acidcomprises formic acid, acetic acid, maleic acid, or any mixture thereof.

25. The method according to any one of paragraphs 1 to 24, wherein theadditive comprises the anhydride.

26. The method according to any one of paragraphs 1 to 25, wherein theadditive comprises the anhydride, and wherein the anhydride comprisesmaleic anhydride, 1,2,4-benzenetricarboxylic anhydride, phthalicanhydride, succinic anhydride, or any mixture thereof.

27. The method according to any one of paragraphs 1 to 26, wherein theadditive comprises the homopolymer.

28. The method according to any one of paragraphs 1 to 27, wherein theadditive comprises the homopolymer, and wherein the homopolymercomprises polyethylene, polypropylene, polystyrene, polyvinylchloride,or any mixture thereof.

29. The method according to any one of paragraphs 1 to 28, wherein theadditive comprises the copolymer.

30. The method according to any one of paragraphs 1 to 29, wherein theadditive comprises the copolymer, and wherein the copolymer comprises analternating copolymer, a periodic copolymer, a statistical copolymer, aterpolymer, a block copolymer, a linear copolymer, a branched copolymer,or any mixture thereof.

31. The method according to paragraph 30, wherein the additive comprisesthe alternating copolymer, and wherein the alternating comprisespoly[styrene-alt-(maleic anhydride)], poly[(ethyleneglycol)-alt-(terephthalic acid; isophthalic acid)], or a mixturethereof.

32. The method according to paragraph 30 or 31, wherein the additivecomprises the periodic copolymer, and wherein the periodic copolymercomprises poly(1,3,6-trioxacyclo octane)poly(oxymethyleneoxyethyleneoxyethylene).

33. The method according to anyone of paragraphs 30 to 32, wherein theadditive comprises the terpolymer, and wherein the terpolymer comprisesacrylonitrile-butadiene-styrene.

34. The method according to anyone of paragraphs 30 to 33, wherein theadditive comprises the statistical copolymer, and wherein thestatistical copolymer comprisespoly(styrene-stat-acrylonitrile-stat-butadiene), poly[(6-aminohexanoicacid)-stat-(7-aminoheptanoic acid)], poly[(4-hydroxybenzoicacid)-co-hydroquinone-co-(terephthalic acid)], poly[styrene-co-(methylmethacrylate)], or any mixture thereof.

35. The method according to anyone of paragraphs 30 to 34, wherein theadditive comprises the block copolymer, and wherein the block copolymercomprises polystyrene-block-polybutadiene-block-polystyrene,poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) blockpolymer, poly[poly(methylmethacrylate)-block-polystyrene-block-poly(methylacrylate)], or anymixture thereof.

36. The method according to anyone of paragraphs 30 to 35, wherein theadditive comprises the linear copolymer, and wherein the linearcopolymer comprises a copolymer of ethylene and one or more C₃ to C₂₀alpha olefin comonomers.

37. The method according to anyone of paragraphs 30 to 36, wherein theadditive comprises the branched copolymer, and wherein branchedcopolymer comprises a branched methacrylate copolymer.

38. The method according to anyone of paragraphs 1 to 4 or 6 to 37,wherein at least a portion of the hydroxybenzene compound and at least aportion of the aldehyde compound are reacted with one another to form aprepolymer, and wherein the prepolymer is further reacted in thepresence of the additive to produce the wet gel.

39. The method according to anyone of paragraphs 1 to 4 or 6 to 38,wherein at least a portion of the hydroxybenzene compound and at least aportion of the aldehyde compound are reacted with one another to form aprepolymer having a refractive index of about 1.1000 to about 1.7000,and wherein the prepolymer is further reacted in the presence of theadditive to produce the wet gel.

40. The method according to anyone of paragraphs 1 to 4 or 6 to 39,wherein at least a portion of the hydroxybenzene compound and at least aportion of the aldehyde compound are reacted with one another to form aprepolymer, and wherein the prepolymer is further reacted with theadditive to produce the wet gel.

41. The method according to anyone of paragraphs 1 to 4 or 6 to 40,further comprising combining at least one solvent with thehydroxybenzene compound, the aldehyde compound, and the additive toproduce the reaction mixture.

42. The method according to paragraph 41, wherein the solvent compriseswater.

43. The method according to anyone of paragraphs 1 to 4 or 6 to 42,further comprising combining at least one polyol with the hydroxybenzenecompound, the aldehyde compound, and the additive to produce thereaction mixture.

44. The method according to paragraph 43, wherein the polyol comprisesethylene glycol.

45. The method according to paragraph 43 or 44, wherein the reactionmixture comprises about 0.1 wt % to about 40 wt % of the polyol, basedon the combined weight of the hydroxybenzene compound, the aldehydecompound, the additive, and the polyol.

46. The method according to anyone of paragraphs 1 to 4 or 6 to 45,further comprising combining at least one modifier with the at least onehydroxybenzene compound, the at least one aldehyde compound, and the atleast one additive comprising the carboxylic acid, the anhydride, thehomopolymer, the copolymer, or any mixture thereof to produce thereaction mixture.

47. The method according to paragraph 46, wherein the modifier compriseslead, tin, antimony, bismuth, arsenic, tungsten, silver, zinc, cadmium,indium, silicon, iron, sulfur, cobalt, nickel, bromine, chlorine,ruthenium, rhodium, platinum, palladium, zirconium, gold, oxidesthereof, or any mixture thereof.

48. The method according to paragraph 46, wherein the at least onemodifier comprises silicon.

49. The method according to paragraph 46, wherein the reaction mixturecomprises about 0.1 wt % to about 95 wt % of the modifier, based on thecombined weight of the hydroxybenzene compound, the aldehyde compound,the additive, and the modifier.

50. The method according to any one of paragraphs 2 to 49, wherein thesolvent comprises water.

51. The method according to any one of paragraphs 2 to 50, wherein thepressure exerted on the wet gel during drying is atmospheric pressure.

52. The method according to any one of paragraphs 2 to 50, wherein thepressure exerted on the wet gel during drying is maintained at or belowatmospheric pressure.

53. The method according to any one of paragraphs 2 to 52, wherein thedried gel has an average pore size of about 10 nm to about 150 nm.

54. The method according to any one of paragraphs 2 to 53, wherein thedried gel has an average pore size of about 51 nm to about 150 nm.

55. The method according to any one of paragraphs 2 to 54, wherein thedried gel has a specific surface area of about 5 m²/g to about 1,500m²/g.

56. The method according to any one of paragraphs 2 to 55, wherein thedried gel has a specific surface area of about 300 m²/g to about 1,000m²/g.

57. The method according to any one of paragraphs 2 to 56, wherein thedried gel has a pore volume of about 0.2 cm³/g to about 2.5 cm³/g.

58. The method according to any one of paragraphs 2 to 57, wherein thedried gel has a pore volume of about 0.35 cm³/g to about 2 cm³/g.

59. The method according to any one of paragraphs 1 or 6 to 58, furthercomprising drying the wet gel to produce a dried gel.

60. The method according to any one of paragraphs 1 or 6 to 58, furthercomprising drying the wet gel to produce a dried gel, wherein a pressureexerted on the wet gel during drying is maintained below a criticalpressure of the solvent.

61. The method according to any one of paragraphs 1 or 6 to 58, furthercomprising drying the wet gel to produce a dried gel, wherein the driedgel has at least one property selected from the group consisting of: anaverage pore size of about 10 nm to about 150 nm, a specific surfacearea of about 5 m²/g to about 1,500 m²/g, and a pore volume of about 0.2cm³/g to about 2.5 cm³/g.

62. The method according to any one of paragraphs 1 or 6 to 58, furthercomprising drying the wet gel to produce a dried gel, wherein a pressureexerted on the wet gel during drying is maintained below a criticalpressure of the solvent, and wherein the dried gel has at least oneproperty selected from the group consisting of: an average pore size ofabout 10 nm to about 150 nm, a specific surface area of about 5 m²/g toabout 1,500 m²/g, and a pore volume of about 0.2 cm³/g to about 2.5cm³/g.

63. The method according to any one of paragraphs 2 to 62, furthercomprising heating the dried gel to a temperature sufficient to producea pyrolized carbon product.

64. The method according to any one of paragraphs 2 to 62, furthercomprising heating the dried gel to a temperature of about 500° C. toabout 2,400° C. to produce a pyrolized carbon product.

65. The method according to any one of paragraphs 1 to 62, furthercomprising heating the wet gel or the dried gel in an inert atmosphereat a temperature of about 500° C. to about 2,400° C. to produce apyrolized carbon product.

66. The method according to any one of paragraphs 1 to 65, furthercomprising heating the wet gel, the dried gel, or the pyrolized carbonproduct in an atmosphere comprising carbon dioxide, carbon monoxide,steam, oxygen, or any mixture thereof at a temperature of about 500° C.to about 1,300° C. to produce an activated carbon product.

67. A method for making a pyrolized carbon particle, comprising:combining a hydroxybenzene compound, an aldehyde compound, and anadditive to produce a reaction mixture, wherein the additive comprises acarboxylic acid, an anhydride, a homopolymer, a copolymer, or anymixture thereof; reacting at least the hydroxybenzene compound and thealdehyde compound to produce a wet gel, wherein the reaction mixturecomprises about 10 wt % to about 65 wt % of the hydroxybenzene compound,about 5 wt % to about 25 wt % of the aldehyde compound, up to about 85wt % of the carboxylic acid, up to about 40 wt % of the anhydride, up toabout 40 wt % of the homopolymer, and up to about 40 wt % of thecopolymer, wherein the reaction mixture comprises about 10 wt % to about90 wt % of the additive, and wherein all weight percent values are basedon the combined weight of the hydroxybenzene compound, the aldehydecompound, and the additive; and heating the wet gel to produce apyrolized carbon product.

68. A method for making a pyrolized carbon particle, comprising:combining at least one solvent, at least one hydroxybenzene compound, atleast one aldehyde compound, and at least one additive to produce areaction mixture, wherein the additive comprises a carboxylic acid, ananhydride, a homopolymer, a copolymer, or any mixture thereof; reactingat least the hydroxybenzene compound and the aldehyde compound toproduce a wet gel; drying the wet gel to produce a dried gel, wherein apressure exerted on the wet gel during drying is maintained below acritical pressure of the solvent, and wherein the dried gel has at leastone property selected from the group consisting of: an average pore sizeof about 10 nm to about 150 nm, a specific surface area of about 5 m²/gto about 1,500 m²/g, and a pore volume of about 0.2 cm³/g to about 2.5cm³/g; and heating the dried gel to produce a pyrolized carbon product.

69. A method for making a pyrolized carbon product, comprising: reactingat least one hydroxybenzene compound and at least one aldehyde compoundto produce a wet gel; drying the wet gel to produce a dried gel, whereina pressure exerted on the wet gel during drying is maintained below acritical pressure of the solvent; and heating the dried gel to produce apyrolized carbon product.

70. A method for making a pyrolized carbon product, comprising: reactingphenol and formaldehyde with one another to produce a wet gel; dryingthe wet gel to produce a dried gel, wherein a pressure exerted on thewet gel during drying is maintained below a critical pressure of thesolvent, and heating the dried gel to produce a pyrolized carbonproduct.

71. A method for making a pyrolized carbon product, comprising: reactingphenol and formaldehyde with one another to produce a wet gel; andheating the wet gel to produce a pyrolized carbon product.

72. The method according to any one of paragraphs 67 to 71, wherein thewet gel, the dried gel, or the pyrolized carbon product is heated in anatmosphere comprising carbon dioxide, carbon monoxide, steam, oxygen, orany mixture thereof at a temperature of about 500° C. to about 2,500° C.to produce an activated carbon product.

73. The method according to any one of paragraphs 67 to 72, wherein thepyrolized carbon product has a pore volume of about 0.03 cm³/g to about2.5 cm³/g.

74. The method according to any one of paragraphs 67 to 73, wherein thepyrolized carbon product has a pore volume of about 0.3 cm³/g to about1.4 cm³/g.

75. The method according to any one of paragraphs 67 to 74, wherein thepyrolized carbon product has a pore size of about 1 nm to about 500 nm.

76. The method according to any one of paragraphs 67 to 75, wherein thepyrolized carbon product has a pore size of about 15 nm to about 90 nm.

77. The method according to any one of paragraphs 67 to 76, wherein thepyrolized carbon product has a specific surface area of about 5 m²/g toabout 1,500 m²/g.

78. The method according to any one of paragraphs 67 to 77, wherein thepyrolized carbon product has a specific surface area of about 140 m²/gto about 500 m²/g.

79. The method according to any one of paragraphs 67 to 78, wherein thepyrolized carbon product has a pore size of about 10 nm to about 100 nmand a pore volume of about 0.2 cm³/g to about 2 cm³/g.

80. The method according to any one of paragraphs 67 to 79, wherein thepyrolized carbon product has a pore size of about 10 nm to about 100 nmand a specific surface area of about 5 m²/g to about 1,500 m²/g.

81. The method according to any one of paragraphs 67 to 80, wherein thepyrolized carbon product has a pore size of about 10 nm to about 100 nm,a specific surface area of about 5 m²/g to about 1,500 m²/g, and a porevolume of about 0.2 cm³/g to about 2 cm³/g.

82. A carbon material comprising a pyrolized carbon product or anactivated carbon product, wherein the carbon material has at least twoof: a pore volume of about 0.03 cm³/g to about 2.5 cm³/g; a pore size ofabout 1 nm to about 500 nm; and a specific surface area of about 5 m²/gto about 1,500 m²/g.

83. A carbon material comprising a pyrolized carbon product or anactivated carbon product, wherein the carbon material has at least twoof: a pore volume of about 0.3 cm³/g to about 1.4 cm³/g, a pore size ofabout 15 nm to about 90 nm, and a specific surface area of about 140m²/g to about 500 m²/g.

84. A carbon material comprising a pyrolized carbon product or anactivated carbon product, wherein the carbon material has a pore volumeof about 0.03 cm³/g to about 2.5 cm³/g; a pore size of about 1 nm toabout 500 nm; and a specific surface area of about 5 m²/g to about 1,500m²/g.

85. A carbon material comprising a pyrolized carbon product or anactivated carbon product, wherein the carbon material has a pore volumeof about 0.3 cm³/g to about 1.4 cm³/g, a pore size of about 15 nm toabout 90 nm, and a specific surface area of about 140 m²/g to about 500m²/g.

86. A method for making an activated carbon particle, comprising:combining a hydroxybenzene compound, an aldehyde compound, and anadditive to produce a reaction mixture, wherein the additive comprises acarboxylic acid, an anhydride, a homopolymer, a copolymer, or anymixture thereof; reacting at least the hydroxybenzene compound and thealdehyde compound to produce a wet gel, wherein the reaction mixturecomprises about 10 wt % to about 65 wt % of the hydroxybenzene compound,about 5 wt % to about 25 wt % of the aldehyde compound, up to about 85wt % of the carboxylic acid, up to about 40 wt % of the anhydride, up toabout 40 wt % of the homopolymer, and up to about 40 wt % of thecopolymer, wherein the reaction mixture comprises about 10 wt % to about90 wt % of the additive, and wherein all weight percent values are basedon the combined weight of the hydroxybenzene compound, the aldehydecompound, and the additive; and heating the wet gel in an atmospherecomprising carbon dioxide, carbon monoxide, steam, oxygen, or anymixture thereof at a temperature of about 500° C. to about 2,500° C. toproduce an activated carbon product.

87. A method for making an activated carbon particle, comprising:combining at least one solvent, at least one hydroxybenzene compound, atleast one aldehyde compound, and at least one additive to produce areaction mixture, wherein the additive comprises a carboxylic acid, ananhydride, a homopolymer, a copolymer, or any mixture thereof; reactingat least the hydroxybenzene compound and the aldehyde compound toproduce a wet gel; drying the wet gel to produce a dried gel, wherein apressure exerted on the wet gel during drying is maintained below acritical pressure of the solvent; and heating the dried gel in anatmosphere comprising carbon dioxide, carbon monoxide, steam, oxygen, orany mixture thereof at a temperature of about 500° C. to about 2,500° C.to produce an activated carbon product.

88. The method according to paragraph 87, wherein the activated carbonproduct has at least one property selected from the group consisting of:an average pore size of about 10 nm to about 150 nm, a specific surfacearea of about 5 m²/g to about 1,500 m²/g, and a pore volume of about 0.2cm³/g to about 2.5 cm³/g.

89. A method for making an activated carbon particle, comprising:reacting at least one hydroxybenzene compound and at least one aldehydecompound to produce a wet gel; drying the wet gel to produce a driedgel, wherein a pressure exerted on the wet gel during drying ismaintained below a critical pressure of the solvent; and heating thedried gel under conditions sufficient to produce an activated carbonproduct.

90. The method according to paragraph 89, wherein the dried gel isheated in an atmosphere comprising carbon dioxide, carbon monoxide,steam, oxygen, or any mixture thereof at a temperature of about 500° C.to about 2,500° C. to produce the activated carbon product.

91. A method for making a wet gel, comprising: combining ahydroxybenzene compound, an aldehyde compound, and an additive toproduce a reaction mixture, wherein the additive comprises a carboxylicacid, an anhydride, a homopolymer, a copolymer, or any mixture thereof;and reacting at least the hydroxybenzene compound and the aldehydecompound to produce a wet gel, wherein the reaction mixture comprisesabout 10 wt % to about 65 wt % of the hydroxybenzene compound, about 5wt % to about 25 wt % of the aldehyde compound, up to about 85 wt % ofthe carboxylic acid, up to about 40 wt % of the anhydride, up to about40 wt % of the homopolymer, and up to about 40 wt % of the copolymer,wherein the reaction mixture comprises about 10 wt % to about 90 wt % ofthe additive, and wherein all weight percent values are based on thecombined weight of the hydroxybenzene compound, the aldehyde compound,and the additive.

92. A method for making a dried gel, comprising: combining a solvent, ahydroxybenzene compound, an aldehyde compound, and an additive toproduce a reaction mixture, wherein the additive comprises a carboxylicacid, an anhydride, a homopolymer, a copolymer, or any mixture thereof;reacting at least the hydroxybenzene compound and the aldehyde compoundto produce a wet gel; and drying the wet gel to produce a dried gel,wherein a pressure exerted on the wet gel during drying is maintainedbelow a critical pressure of the solvent, and wherein the dried gel hasat least one property selected from the group consisting of: an averagepore size of about 10 nm to about 150 nm, a specific surface area ofabout 5 m²/g to about 1,500 m²/g, and a pore volume of about 0.2 cm³/gto about 2.5 cm³/g.

93. A method for making a dried gel, comprising: determining one or moredesired properties of a dried gel selected from the group consisting of:an average pore size of about 10 nm to about 150 nm, a specific surfacearea of about 5 m²/g to about 1,500 m²/g, and a pore volume of about 0.2cm³/g to about 2.5 cm³/g; combining a solvent, a hydroxybenzenecompound, an aldehyde compound, and an additive to produce a reactionmixture, wherein the additive comprises a carboxylic acid, an anhydride,a homopolymer, a copolymer, or any mixture thereof; reacting at leastthe hydroxybenzene compound and the aldehyde compound to produce a wetgel; and drying the wet gel to produce a dried gel, wherein a pressureexerted on the wet gel during drying is maintained below a criticalpressure of the solvent, and wherein the amount of the hydroxybenzenecompound, the amount of the aldehyde compound, and the amount of theadditive are controlled to produce the dried gel having the one or moredesired properties.

94. The method according to any one of paragraphs 67, 68, or 91 to 93,wherein the reaction mixture comprises about 25 wt % to about 90 wt % ofthe additive, based on the combined weight of the hydroxybenzenecompound, the aldehyde compound, and the additive.

95. The method according to any one of paragraphs 67, 68, or 91 to 94,wherein the reaction mixture comprises about 25 wt %, about 30 wt %, orabout 35 wt % to about 50 wt %, about 60 wt %, about 70 wt %, about 80wt %, or about 90 wt % of the additive, based on the combined weight ofthe hydroxybenzene compound, the aldehyde compound, and the additive.

96. The method according to any one of paragraphs 67, 68, or 91 to 95,wherein the reaction mixture comprises about 25 wt % to about 70 wt % ofthe carboxylic acid, based on the combined weight of the hydroxybenzenecompound, the aldehyde compound, and the additive.

97. The method according to any one of paragraphs 67, 68, or 91 to 96,wherein the reaction mixture comprises about 0.5 wt % to about 10 wt %of the anhydride, based on the combined weight of the hydroxybenzenecompound, the aldehyde compound, and the additive.

98. The method according to any one of paragraphs 67, 68, or 91 to 97,wherein the reaction mixture comprises about 0.5 wt % to about 10 wt %of the homopolymer, based on the combined weight of the hydroxybenzenecompound, the aldehyde compound, and the additive.

99. The method according to any one of paragraphs 67, 68, or 91 to 98,wherein the reaction mixture comprises about 1 wt % to about 10 wt % ofthe copolymer, based on the combined weight of the hydroxybenzenecompound, the aldehyde compound, and the additive.

100. The method according to any one of paragraphs 67, 68, or 91 to 99,wherein the reaction mixture comprises about 30 wt % to about 70 wt % ofthe carboxylic acid, about 0.1 wt % to about 10 wt % of the anhydride,and about 0.1 wt % to about 8 wt % of the copolymer, based on thecombined weight of the hydroxybenzene compound, the aldehyde compound,and the additive.

101. The method according to any one of paragraphs 67, 68, or 91 to 100,wherein the additive comprises the copolymer, and wherein the copolymercomprises an alternating copolymer, a periodic copolymer, a statisticalcopolymer, a terpolymer, a block copolymer, a linear copolymer, abranched copolymer, or any mixture thereof.

102. The method according to any one of paragraphs 67, 68, or 91 to 101,wherein at least a portion of the hydroxybenzene compound and at least aportion of the aldehyde compound are reacted with one another to form aprepolymer, and wherein the prepolymer is reacted in the presence of theadditive to produce the wet gel.

103. The method according to any one of paragraphs 67, 68, or 91 to 102,wherein at least a portion of the hydroxybenzene compound and at least aportion of the aldehyde compound are reacted with one another to form aprepolymer, and wherein the prepolymer is reacted with the additive toproduce the wet gel.

104. The method according to any one of paragraphs 67, 68, or 91 to 103,further comprising combining at least one polyol with the hydroxybenzenecompound, the aldehyde compound, and the additive to produce thereaction mixture, wherein the reaction mixture comprises about 0.1 wt %to about 40 wt % of the polyol, based on the combined weight of thehydroxybenzene compound, the aldehyde compound, the additive, and thepolyol.

105. The method according to any one of paragraphs 67, 68, or 91 to 104,further comprising combining at least one modifier with thehydroxybenzene compound, the aldehyde compound, and the additive toproduce the reaction mixture, wherein the modifier comprises lead, tin,antimony, bismuth, arsenic, tungsten, silver, zinc, cadmium, indium,silicon, iron, sulfur, cobalt, nickel, bromine, chlorine, ruthenium,rhodium, platinum, palladium, zirconium, gold, oxides thereof, or anymixture thereof, and wherein the reaction mixture comprises about 0.1 wt% to about 95 wt % of the modifier, based on the combined weight of thehydroxybenzene compound, the aldehyde compound, the additive, and themodifier.

106. The method according to any one of paragraphs 91 to 105, furthercomprising drying the wet gel to produce a dried gel.

107. The method according to any one of paragraphs 91 to 106, furthercomprising drying the wet gel to produce a dried gel, wherein the driedgel has at least one property selected from the group consisting of: anaverage pore size of about 10 nm to about 150 nm, a specific surfacearea of about 5 m²/g to about 1,500 m²/g, and a pore volume of about 0.2cm³/g to about 2.5 cm³/g.

108. The method according to any one of paragraphs 91 to 107, furthercomprising combining at least one solvent with the hydroxybenzenecompound, the aldehyde compound, and the additive to produce thereaction mixture; and drying the wet gel to produce a dried gel, whereina pressure exerted on the wet gel during drying is maintained below acritical pressure of the solvent.

109. The method according to any one of paragraphs 91 to 108, whereinthe dried gel has at least one property selected from the groupconsisting of: an average pore size of about 10 nm to about 150 nm, aspecific surface area of about 5 m²/g to about 1,500 m²/g, and a porevolume of about 0.2 cm³/g to about 2.5 cm³/g.

110. The method according to any one of paragraphs 67, 68, or 91 to 109,wherein the hydroxybenzene compound comprises phenol, resorcinol,cresol, catechol, hydroquinone, phloroglucinol, or any mixture thereof,and wherein the aldehyde compound comprises formaldehyde, acetaldehyde,propionaldehyde, butyraldehyde, furfuraldehyde, glucose, benzaldehyde,cinnamaldehyde, or any mixture thereof.

111. The method according to any one of paragraphs 67, 68, or 91 to 110,wherein the hydroxybenzene compound comprises phenol, resorcinol,cresol, catechol, hydroquinone, phloroglucinol, or any mixture thereof,wherein the aldehyde compound comprises formaldehyde, acetaldehyde,propionaldehyde, butyraldehyde, furfuraldehyde, glucose, benzaldehyde,cinnamaldehyde, or any mixture thereof, and wherein the additivecomprises acetic acid, citric acid, and maleic anhydride.

112. A pyrolized carbon product having at least two of: a pore volume ofabout 0.03 cm³/g to about 2.5 cm³/g; a pore size of about 1 nm to about500 nm; and a specific surface area of about 5 m²/g to about 1,500 m²/g.

113. A pyrolized carbon product having at least two of: a pore volume ofabout 0.3 cm³/g to about 1.4 cm³/g, a pore size of about 15 nm to about90 nm, and a specific surface area of about 140 m²/g to about 500 m²/g.

114. A pyrolized carbon product having a pore volume of about 0.03 cm³/gto about 2.5 cm³/g; a pore size of about 1 nm to about 500 nm; and aspecific surface area of about 5 m²/g to about 1,500 m²/g.

115. A pyrolized carbon product having a pore volume of about 0.3 cm³/gto about 1.4 cm³/g, a pore size of about 15 nm to about 90 nm, and aspecific surface area of about 140 m²/g to about 500 m²/g.

116. An activated carbon product having at least two of: a pore volumeof about 0.03 cm³/g to about 2.5 cm³/g; a pore size of about 1 nm toabout 500 nm; and a specific surface area of about 5 m²/g to about 1,500m²/g.

117. A activated carbon product having at least two of: a pore volume ofabout 0.3 cm³/g to about 1.4 cm³/g, a pore size of about 15 nm to about90 nm, and a specific surface area of about 140 m²/g to about 500 m²/g.

118. A activated carbon product having a pore volume of about 0.03 cm³/gto about 2.5 cm³/g; a pore size of about 1 nm to about 500 nm; and aspecific surface area of about 5 m²/g to about 1,500 m²/g.

119. A activated carbon product having a pore volume of about 0.3 cm³/gto about 1.4 cm³/g, a pore size of about 15 nm to about 90 nm, and aspecific surface area of about 140 m²/g to about 500 m²/g.

120. The activated carbon product according to any one of paragraphs 116to 119, wherein the activated carbon product is produced by heating apyrolized carbon product in an atmosphere comprising carbon dioxide,carbon monoxide, steam, oxygen, or any mixture thereof to a temperatureof about 500° C. to about 1,300° C.

Certain embodiments and features have been described using a set ofnumerical upper limits and a set of numerical lower limits. It should beappreciated that ranges including the combination of any two values,e.g., the combination of any lower value with any upper value, thecombination of any two lower values, and/or the combination of any twoupper values are contemplated unless otherwise indicated. Certain lowerlimits, upper limits and ranges appear in one or more claims below. Allnumerical values are “about” or “approximately” the indicated value, andtake into account experimental error and variations that would beexpected by a person having ordinary skill in the art.

Various terms have been defined above. To the extent a term used in aclaim is not defined above, it should be given the broadest definitionpersons in the pertinent art have given that term as reflected in atleast one printed publication or issued patent. Furthermore, allpatents, test procedures, and other documents cited in this applicationare fully incorporated by reference to the extent such disclosure is notinconsistent with this application and for all jurisdictions in whichsuch incorporation is permitted.

While the foregoing is directed to embodiments of the present invention,other and further embodiments of the invention may be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

What is claimed is:
 1. A method for making a wet gel, comprising:combining a hydroxybenzene compound, an aldehyde compound, and anadditive to produce a reaction mixture, wherein the additive comprises acarboxylic acid and an anhydride; and reacting at least thehydroxybenzene compound and the aldehyde compound to produce a wet gel,wherein the reaction mixture comprises about 10 wt % to about 65 wt % ofthe hydroxybenzene compound, about 5 wt % to about 25 wt % of thealdehyde compound, about 0.1 wt % to about 85 wt % of the carboxylicacid, and about 0.1 wt % to about 40 wt % of the anhydride, wherein thereaction mixture comprises about 10 wt % to about 90 wt % of theadditive, and wherein all weight percent values are based on thecombined weight of the hydroxybenzene compound, the aldehyde compound,and the additive; and drying the wet gel to produce a dried gel, whereinthe dried gel has at least one property selected from the groupconsisting of: an average pore size of about 10 nm to about 150 nm, aspecific surface area of about 5 m²/g to about 1,500 m²/g, and a porevolume of about 0.2 cm³/g to about 2.5 cm³/g.
 2. The method of claim 1,further comprising combining at least one solvent with thehydroxybenzene compound, the aldehyde compound, and the additive toproduce the reaction mixture, wherein a pressure exerted on the wet gelduring drying is maintained below a critical pressure of the solvent. 3.The method of claim 1, wherein the hydroxybenzene compound comprisesphenol, resorcinol, cresol, catechol, hydroquinone, phloroglucinol, orany mixture thereof, and wherein the aldehyde compound comprisesformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde,furfuraldehyde, glucose, benzaldehyde, cinnamaldehyde, or any mixturethereof.
 4. The method of claim 1, wherein the hydroxybenzene compoundcomprises phenol, resorcinol, cresol, catechol, hydroquinone,phloroglucinol, or any mixture thereof, wherein the aldehyde compoundcomprises formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde,furfuraldehyde, glucose, benzaldehyde, cinnamaldehyde, or any mixturethereof, and wherein the additive comprises acetic acid, citric acid,and maleic anhydride.
 5. The method of claim 1, further comprising:combining at least one solvent with the hydroxybenzene compound, thealdehyde compound, and the additive to produce the reaction mixture,wherein: a pressure exerted on the wet gel during drying is maintainedbelow a critical pressure of the solvent, the hydroxybenzene compoundcomprises phenol, resorcinol, cresol, catechol, hydroquinone,phloroglucinol, or any mixture thereof, the aldehyde compound comprisesformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde,furfuraldehyde, glucose, benzaldehyde, cinnamaldehyde, or any mixturethereof, the additive comprises acetic acid, citric acid, and maleicanhydride, and the solvent comprises water.
 6. A method for making adried gel, comprising: combining a solvent, a hydroxybenzene compound,an aldehyde compound, and an additive to produce a reaction mixture,wherein the additive comprises a carboxylic acid and an anhydride;reacting at least the hydroxybenzene compound and the aldehyde compoundto produce a wet gel; and drying the wet gel to produce a dried gel,wherein a pressure exerted on the wet gel during drying is maintainedbelow a critical pressure of the solvent, and wherein the dried gel hasat least one property selected from the group consisting of: an averagepore size of about 10 nm to about 150 nm, a specific surface area ofabout 5 m²/g to about 1,500 m²/g, and a pore volume of about 0.2 cm³/gto about 2.5 cm³/g.
 7. A method for making a dried gel, comprising:determining one or more desired properties of a dried gel selected fromthe group consisting of: an average pore size of about 10 nm to about150 nm, a specific surface area of about 5 m²/g to about 1,500 m²/g, anda pore volume of about 0.2 cm³/g to about 2.5 cm³/g; combining asolvent, a hydroxybenzene compound, an aldehyde compound, and anadditive to produce a reaction mixture, wherein the additive comprises acarboxylic acid and an anhydride; reacting at least the hydroxybenzenecompound and the aldehyde compound to produce a wet gel; and drying thewet gel to produce a dried gel, wherein a pressure exerted on the wetgel during drying is maintained below a critical pressure of thesolvent, and wherein the amount of the hydroxybenzene compound, theamount of the aldehyde compound, and the amount of the additive arecontrolled to produce the dried gel having the one or more desiredproperties.
 8. The method of claim 1, wherein the reaction mixturecomprises about 25 wt % to about 70 wt % of the carboxylic acid andabout 0.5 wt % to about 10 wt % of the anhydride, based on the combinedweight of the hydroxybenzene compound, the aldehyde compound, and theadditive.
 9. The method of claim 1, wherein the anhydride comprisesmaleic anhydride, 1,2,4-benzenetricarboxylic anhydride, phthalicanhydride, succinic anhydride, or any mixture thereof.
 10. The method ofclaim 1, wherein the carboxylic acid comprises a polycarboxylic acid.11. The method of claim 10, wherein the polycarboxylic acid comprisescitric acid.
 12. The method of claim 1, wherein the reaction mixturefurther comprises a polyol.
 13. The method of claim 12, wherein thepolyol comprises diethanolamine, triethanolamine, ethyl diethanolamine,methyl diethanolamine, or any mixture thereof.
 14. The method of claim1, wherein the reaction mixture further comprises about 1 wt % to about5 wt % of water, based on a combined weight of the hydroxybenzenecompound, the aldehyde compound, the additive, and the water.
 15. Themethod of claim 1, wherein the reaction mixture further comprises about0.01 wt % to about 90 wt % of a modifier, based on a combined weight ofthe hydroxybenzene compound, the aldehyde compound, the additive, andthe modifier, and wherein the modifier comprises lead, tin, antimony,bismuth, arsenic, tungsten, silver, zinc, cadmium, indium, silicon,iron, sulfur, cobalt, nickel, bromine, chlorine, ruthenium, rhodium,platinum, palladium, zirconium, gold, or any mixture thereof.
 16. Themethod of claim 1, wherein at least a portion of the hydroxybenzenecompound and at least a portion of the aldehyde compound are reactedwith one another to form a prepolymer, and wherein the prepolymer isreacted in the presence of the additive to produce the wet gel.
 17. Themethod of claim 1, wherein at least a portion of the hydroxybenzenecompound and at least a portion of the aldehyde compound are reactedwith one another to form a prepolymer, and wherein the prepolymer isreacted with the additive to produce the wet gel.
 18. The method ofclaim 1, wherein the additive further comprises about 0.5 wt % to about10 wt % of a homopolymer, based on a combined weight of thehydroxybenzene compound, the aldehyde compound, and the additive, andwherein the homopolymer comprises polyethylene, polypropylene,polystyrene, polyvinylchloride, or a mixture thereof.
 19. The method ofclaim 1, wherein the additive further comprises about 0.1 wt % to about10 wt % of a copolymer, based on the combined weight of thehydroxybenzene compound, the aldehyde compound, and the additive, andwherein the copolymer comprises poly[styrene-alt-(maleic anhydride)],poly[(ethylene glycol)-alt-(terephthalic acid; isophthalic acid)],poly(1,3,6-trioxacyclooctane) poly(oxymethyleneoxyethyleneoxyethylene),poly(styrene-stat-acrylonitrile-stat-butadiene), poly[(6-aminohexanoicacid)-stat-(7-aminoheptanoic acid)], poly[(4-hydroxybenzoicacid)-co-hydroquinone-co-(terephthalic acid)], poly[styrene-co-(methylmethacrylate)], acrylonitrile-butadiene-styrene terpolymer,polystyrene-block-polybutadiene-block-polystyrene, poly(ethyleneglycol)-poly(propylene glycol)-poly(ethylene glycol) block polymer,poly[poly(methyl methacrylate)-block-polystyrene-block-poly(methylacrylate)], a copolymer of ethylene and one or more C₃ to C₂₀ alphaolefin comonomers, a branched methacrylate copolymer, or any mixturethereof.
 20. The method of claim 1, wherein: the reaction mixturefurther comprises a solvent, the hydroxybenzene compound comprisesphenol, resorcinol, or a mixture thereof, the aldehyde compoundcomprises formaldehyde, the carboxylic acid comprises acetic acid, theanhydride comprises maleic anhydride, the solvent comprises water, thereaction mixture comprises about 25 wt % to about 70 wt % of thecarboxylic acid and about 0.5 wt % to about 10 wt % of the anhydride,based on the combined weight of the hydroxybenzene compound, thealdehyde compound, and the additive, the reaction mixture comprisesabout 1 wt % to about 5 wt % of the solvent, based on a combined weightof the hydroxybenzene compound, the aldehyde compound, the additive, andthe solvent, and a pressure exerted on the wet gel during drying ismaintained below a critical pressure of the solvent.